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Introduction
The general electronic configuration of transition element is (n-1)d1-10 ns0, 1 or 2
The transition elements have an incompletely filled d-level. Since Zn, Cd, Hg elements have d10 configuration and are not
considered as transition elements but they are d-block elements.

Electronic Configuration

Metallic Character :
In d-block elements the last but one (i.e. the penultimate) shell of electrons is expanding. Thus they have many physical
and chemical properties in common.
Hence nearly all the transition elements display typical metallic properties such as high tensile strength, ductility,
malleability, high thermal and electrical conductivity and metallic lustre. With the exceptions of Zn,Cd, Hg and Mn, they
have one or more typical metallic structures at normal temperatures.
They have high enthalpies of atomisation which are shown in figure given below. The maxima at about the middle of each

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series indicate that one unpaired electron per d orbital is particularly favourable of strong interatomic interaction. In
general, greater the number of valence electrons, stronger is the resultant bonding. Cr, Mo and W have maximum
number of unpaired electrons and therefore, these are very hard metals and have maximum enthalpies of atomization.
They are hard, malleable and ductile (except Hg). IB group elements Cu, Ag and Au are most ductile and soft.
These are good conducter of heat and electricity (due to free e–) Elements of IB group are most conductive in nature.Their
order of conductivity is Ag > Cu > Au > Al.
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 Standard oxidation potential (SOP) of Cu is minimum in the 3d series so it is least reducing elements in 3d series.
Au is the least reducing element in the d-block because of highest +ve value of Standard reduction potential.
The poor reducing capacity of the transition metal is due to high heats of vaporization, high ionization potential and low
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heat of hydration of their ions, because reduction potential depends upon all these three factors.

Size of Atoms and Ions : A-/ - H; X: //:TI.k#;.f/

The covalent radii of the elements decreases from left to right across a row in the transition series, until near the end
when the size increases slightly. The decrease in size is small after mid way.
The atomic radii, in general, increase down the group. The atomic radii of second series are larger than those of first
transition series. But the atomic radii of the second and third transition series are almost the same. = G0F J0pM0
This phenomenon is associated with the intervention of the 4f orbitals which must be filled before the 5d series of
elements begin. The filling of 4f before 5d orbital results in a regular decrease in atomic radii called Lanthanoid
contraction.

Melting & Boiling Points :

The melting and boiling points of the transition series elements are generally very high. The melting points of the transi-
tion elements rise to a maximum and then fall as the atomic number increases. Manganese and technetium have
abnormally low melting points. Strong metallic bonds between the atoms of these elements attribute to their high melting
and boiling points. In a particular series, the metallic strength increases upto the middle with increasing number of
unpaired electrons i.e up to d5. After chromium, the number of unpaired electrons goes on decreasing. Accordingly, the
melting points decrease after middle (Cr) because of increasing pairing of electrons.
The dip in melting points of Mn and Tc can be attributed to their stable electronic configurations (half filled 3d 5 and fully
filled 4s2 ). Due to this stable electronic configuration, the delocalisation of electrons may be less and thus the metallic
bond is much weaker than preceding elements.

Density :
The densities of the second row are high and third row values are even higher. $ G 0 % J 0 % A 0
Across a period from left to right atomic volumes decrease and atomic masses increase. Hence the densities also
increase across a period.

K
The last element zinc
c is an exception, having large atomic volume and hence lower density.
Os (22.57 gm cm ) and Ir (22.61 gm cm—3) have highest density.
—3

In 3d series highest density – Cu lowest density – Sc

Some important orders of density
Fe < Ni < Cu Fe < Cu < Au Fe < Hg < Au

Ionisation Energies or Ionisation Enthalpies :

Generally, the lower valent states are ionic and the higher valent states are covalent. Across a period from left to right
ionisation energies gradually increase with increase in atomic number.
the difference in the ionisation energies between any two successive d-block elements is very much less than the
difference in case of successive s-block or p-block elements. #/ (
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The first ionisation energy of Zn, Cd, and Hg are very high because of their fully filled (n–1) d ns configuration.
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IInd ionisation energy of Cr > Mn and Cu > Zn TI4-U
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Graph Showing Trends in Ionisation Energies
Oxidation States :
The transition metals exhibit a large number of oxidation states.
This is due to the participation of inner (n – 1) d-electrons in addition to outer ns-electrons because, the energies of the
ns and (n – 1) d-sub-shells are nearly same.

Outer %4kk4<
Element electronic Oxidation states
configuration
6A Sc 3d14s2 +3
2 2
Ti 3d 4s +2, +3, +4
V4/ s 3 2
V 3d 4s +2, +3, +4, +5
Cr 3d54s1 +2, +3, (+4), (+5), +6
5 2
Mn 3d 4s +2, +3, +4, (+5), +6, +7
6 2
Fe 3d 4s +2, +3, (+4), (+5), (+6)
Co 3d74s2 +2, +3, (+4)
8 2
Ni 3d 4s +2, +3, +4
Cu 3d104s1 +1, +2
10 2
Zn 3d 4s +2
Different oxidation states of first transition series

The highest oxidation states are found in compounds of fluorides and oxides because fluorine and oxygen are most
electronegative elements.
Except scandium, the most common oxidation state of the first row transition elements is +2 which arises due to loss of
two 4s-electrons. This means that after scandium 3d-orbitals become more stable and, therefore, are lower in energy
than the 4s-orbitals. As a result, electrons are first removed from 4s-orbitals.
Within a group, the maximum oxidation state increase with atomic number. For example, iron (group 8) shows common
oxidation states of +2 and +3 but ruthenium and osmium in the same group form compounds in the +4, +6 and +8
oxidation states.
In lower oxidation state transition elements form ionic compounds and in higher oxidation state their compounds are
covalent.
They also shows zero oxidation state in their carbonyl compounds like Ni(CO)4.
Usually transition metal ions in their lower oxidation state act as reducing agents and in higher oxidation state they are
oxidising agents.
Ex. Sc+2, Ti+2, V+2, Fe+2, Co+2 etc are reducing agents
c
Cr+6, Mn+7, Mn+6, Mn+5, Mn+4 etc are oxidising agents.
The relative stabilities of various oxidation states of 3d-series element can be correlated with the extra stability of 3d°,3d 5
& 3 d10 configuration to some extent.
Ex. Stability of Ti4+ (3d0) > Ti3 + (3d1 ) Mn2+ (3d5) > Mn3+ (3d4)

Standard Electrode Potentials :

Ni Ni2+ + 2e– I.E. = 2.49 × 103 kJ mol–1
Pt Pt + 2e
2+ –
I.E. = 2.66 × 103 kJ mol–1
Therefore, ionization of nickel to Ni2+ is energetically favourable as compared to that of platinum. Thus, the nickel (II)
compounds are thermodynamically more stable than platinum (II) compounds. On the other hand, the sum of first four
ionisation enthalpies is less for platinum than for nickel as :
Ni Ni4+ + 2e– I.E. = 11.29 × 103 kJ mol–1
Pt Pt + 2e
4+ –
I.E. = 9.36 × 103 kJ mol–1
Thus, the platinum (IV) compounds are relatively more stable than nickel (IV) compounds.
 Electrode Potentials :

The oxidation potential which gives the tendency of the overall change to occur, depends upon the net effect of these
three steps. The overall energy change is

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H = subH + IE + hydH

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Thermochemical data (kJ mol–1) for the first row Transition Elements and the Standard Electrode potentials for the
Reduction of MII to M.
8Z
f H1 1H2
2+
Element (M) a Hq (M) hyd H (M ) E /V
Ti 469 661 1310 -1866 -1.63
V 515 648 1370 -1895 -1.18
Cr 398 653 1590 -1925 -0.90
Mn 279 716 1510 -1862 -1.18
Fe 418 762 1560 -1998 -0.44
Co 427 757 1640 -2079 -0.28
Ni 431 736 1750 -2121 -0.25
Cu 339 745 1960 -2121 0.34
Zn 130 908 1730 -2059 -0.76

Trends in Stability of Higher Oxidation States :

1. In metal halides
These reactions have very high heat of reaction. The halogens react in the following decreasing order; F 2 > Cl2 > Br2 > I2
Oxidation
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Number
+6 CrF6
+5 VF5 CrF5

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+3 ScX3 TiX3 VX3 CrF3 MnF3 FeX3 CoF3
c
+2 TiX2 VX2 CrF2 MnX2 FeX2 CoX2 NiX2 CuX2b ZnX2
Y c
+1 h> CuX K h>
a b c
where X = F, Cl, Br, I, X = F, Cl, Br, X = F, Cl, X = Cl, Br, I

Halides of first transition series

(a) In general, the second and third transition series elements exhibit higher coordination number and their higher
oxidation states are more stable than the corresponding first transition series elements.
(b) The +7 oxidation state for Mn is not shown by simple halides. However, MnO 3F is known in which the oxidation
state of Mn is +7.
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(c) The tendency of fluorine to stabilise the highest oxidation state is due to either higher lattice enthalpy as in case
of CoF3 or higher bond enthalpy due to higher covalent bonds e.g., VF 5 and CrF6.
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(d) All copper (II) halides are known except the iodide. This is because, Cu oxidises I to I2.
2+ –
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2Cu2+ + 4I– Cu2I2(s) + I2
(d) Copper in +2 oxidation state is more stable than in +1 oxidation state. This can be explained on the basis of much
larger negative hydration enthalpy ( hydH ) of Cu2+ (aq) than Cu+, which is much more than compensates for the
large energy required to remove the second electron i.e., second ionisation enthalpy of copper.
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2. In metal oxides and oxocations E

(a) manganese forms highest fluoride as MnF4 whereas the highest oxide is Mn2O7. This is due to the fact that oxygen
has great ability to form multiple bonds to metals. In the covalent oxide. Mn2O7, each Mn is tetrahedrally surrounded
by oxygen atoms and has Mn–O–Mn bridge. W<#;&.- /;9H<W;& 6
(b) As the oxidation number of a metal increases, the ionic character of their oxides decrease. For example, in case
of Mn, Mn2O7 is a covalent green oil. In these higher oxides the acidic character is predominant. Thus CrO3 gives
H2CrO4 and H2Cr2O7 and Mn2O7 gives HMnO4. V2O5 is, however amphoteric though mainly acidic and with alkalies
as well as acids gives VO43– and VO2+ respectively.

Formation of Coloured Ions :

In the case of compounds of transition metals, the energies of the five d-orbitals in the same sub-shell do not remain
equal. Under the influence of approaching ions towards the central metal ion, the d-orbitals of the central metal split into
different energy levels. This phenomenon is called crystal field splitting.
In the case of the transition metal ions, the electron can be easily promoted from one energy level to another in the same
d-sub-shell. These are called d-d transitions.
when white light falls on a transition metal compound, some of its energy corresponding to a certain colour, is absorbed
and the electron gets raised from lower energy set of orbitals to higher energy set of orbitals as shown below

Figure showing electronic transition from t2g to eg orbitals

The excess of other colours constituting white light are transmitted and the compound appears coloured. The observed
colour of a substance is always complementary colour of the colour which is absorbed by the substance.
Ion Outer Configuration Colour of the ion
Sc (III), Ti (IV) 3d0 Colourless
Ti (III) 3d1 Purple
V (IV) 3d1 Blue
V (III) 3d2 Green
Cr (III) 3d3 Green
Mn (III) 3d4 Violet
Cr (II) 3d4 Blue
Mn (II) 3d5 Pink
Fe (III) 3d5 Yellow
Fe (II) 3d6 Green
Co (III) 3d6 Blue
Co (II) 3d7 Pink
Ni (II) 3d8 Green
Cu (II) 3d9 Blue
Cu (I) 3d10 Colourless
Zn (II) 3d10 Colourless
Colour of different hydrated transition metal ions

Transition metal ions which do not have any unpaired elctrons in their 'd' orbitals like 3d 0 and 3d10 configurations, do not
exhibit any colour property.
Ex. Sc+3 : [Ar]3d0, Cu+1 : [Ar]3d10, Ti+4 : [Ar]3d0 etc are colourless ions.
KMnO4 (dark pink), K2Cr2O7 (orange) having d° configuration but they are coloured due to charge transfer spectrum and
charge is transfered from anion to cation.
Magnetic Properties
Paramagnetic substances. The substances which are attracted by magnetic field are called paramagnetic substances
and this character arises due to the presence of unpaired electrons in the atomic orbitals.
Diamagnetic substances. The substances which are repelled by magnetic field are called diamagnetic substances and
this character arises due to the presence of paired electrons in the atomic orbitals.

= n (n 2) B.M.
where n is the number of unpaired electrons and is magnetic moment in Bohr magneton (BM) units.
In addition to paramagnetic and diamagnetic substances, there are a few substances such as iron metal, iron oxide
which are highly magnetic (about 1000 times more than ordinary metals). These are very strongly attracted by applied
magnetic field and retained their magnetism when removed from the field are called ferromagnetic substances.

Formation of complexes :
The great tendency of transition metal ions to form complexes is due to :
(a) small size of the atoms and ions,
(b) high nuclear charge and
(c) availability of vacant d-orbitals of suitable energy to accept lone pairs of electrons donated by ligands.

Formation of Interstitial Compounds :

Transition metals form interstitial compounds with elements such as hydrogen, boron, carbon and nitrogen. The small
atoms of these non-metallic elements (H, B, C, N, etc.) get trapped in vacant spaces of the lattices of the transition metal
atoms as shown below.

Figure showing formation of interstitial compounds

The common examples of interstitial compounds of transition metals are TiC, Mn4N, Fe3H, TiH2 etc. It may be noted that
these formula do not correspond to any normal oxidation state of the metal. Generally, the nonstoichiometric materials
are obtained having the composition as TiH1.7, VH0.56, etc.
As a result of the filling up of the interstitial spaces, the transition metals become rigid and hard.
The smaller sized elements are held in interstitial spaces of transition elements by weak Vander Waals forces of
attractions.
The interstitial compounds have essentially the same chemical properties as the parent metals but they differ in physical
properties such as density and hardness. The process of adsorption of excess of H atom by the transition metals like Pd,
Pt etc is called occlusion.
The general characteristic physical and chemical properties of these compounds are :
(a) They have high melting points which are higher than those of pure metals.
(b) They retain metallic conductivity i.e. of pure metals.
(c) They are very hard and some borides have hardness as that of diamond.
(d) They are chemically inert.
Catalytic properties :
The catalytic property of transition metals is due to their tendency to form reaction intermediates with suitable reactants.
These intermediates give reaction paths of lower activation energy and, therefore increase the rate of the reaction.
These reaction intermediates readily decompose yielding the products and regenerating the original substance. The
transition metals form these reaction intermediates due to the presence of vacant orbitals or their tendency to form
variable oxidation states.
O
-#;#IQ/; ) V2O5 + SO2 (catalyst)
' SO3 + V2O4 (divanadium tetroxide)
2V2O4 + O2 2V2O5
When transition elements and their compounds are in powdered state, their catalytic properties exhibited will be to a
greater extent. This is due to greater surface area available in the powdered state.

Alloy Formation :
Alloys are homogeneous solid solutions in which the atoms of one metal are distributed randomly among the atoms of
the other metal. The alloys are generally formed by those atoms which have metallic radii within about 15% of each other.
The transition metals are quite similar in size and, therefore, the atoms of one metal can substitute the atoms of other
metal in its crystal lattice.
Most common known alloys are ferrous alloys. Chromium, manganese, vanadium, tungsten, molybdenum etc. are used
to produce variety of steels and stainless steel.

Figure showing formation of alloys

Preparation & Properties of Some Important D-Block Metal Compounds :

A. COMPOUND OF IRON : #T#/&H0 c

1. Ferrous Sulphate, FeSO4.7H2O (Green vitriol)

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3FeS2 + 2H2O + 11O2 FeSO4 + Fe2(SO4)3 + 2H2SO4

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Fe2(SO4)3 + Fe 3FeSO4
Properties 6
(a) Physical : (i) Hydrated ferrous sulphate is a green crystalline compound, effloresces] on exposure to air.
Anhydrous FeSO4 is colourless. &HH

(ii) It is commonly known as harakasis.

(b) Chemical : (i) On exposure to atmosphere, it turns brownish-yellow due to the formation of basic ferric
sulphate.
4FeSO4 + 2H2O + O2 4Fe(OH) . SO4 (basic ferric sulphate)
; (wb P'G
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140 C 300 º C High
(ii) FeSO4 . 7H2O FeSO4. H2O 2FeSO4 Fe2O3 + SO2 + SO3
Temp.

(iv) FeSO4 + 6KCN K4[Fe(CN)6] + K2SO4

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AuCl3 + 3FeSO4 Au + Fe2(SO4)3 + FeCl3 S

6HgCl2 + 6FeSO4 3Hg2Cl2 + 2Fe2(SO4)3 + 2FeCl3

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 (vi) A cold solution of ferrous sulphate absorbs nitric oxide forming dark brown addition
compound, nitroso ferrous sulphate.
FeSO4 + NO FeSO4 · NO
Nitroso ferrous sulphate (Brown)
The NO gas is evolved when the solution is heated.

2. Ferric Oxide, Fe2O3

Preparation
(i) 2FeSO4 Fe2O3 + SO2 + SO3
(ii) 4FeS + 7O2 2Fe2O3 + 4SO2

Properties
(a) Physical : It is a deep red powder and is insoluble in water.
(b) Chemical : (i) Amphoteric nature of iron (III) oxide.
Fe2O3 + 6HCl 2FeCl3 + 3H2O
fusion
Fe2O3 + 2NaOH H2O + 2NaFeO2
w
1 G 'm '

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1300 º C
(ii) 6Fe2O3 4Fe3O4 + O2

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3. Ferric Chloride, FeCl3
Preparation
(a) Anhydrous FeCl3 :

(i) 2Fe + 3Cl2(dry) 2FeCl3

(ii) FeCl3 . 6H2O + 6SOCl2 FeCl3 + 12HCl + 6SO2
(b) Hydrated FeCl3 :
(i) Fe2(CO3)3 + 6HCl 2FeCl3 + 3H2O + 3CO2
(ii) 2Fe + 4HCl + Cl2 2FeCl3 + 2H2
All solutions of FeCl3 obtained in above chemical reactions on crystallisation gives hydrated
FeCl3.6H2O.
Properties
(a) Physical : Anhydrous ferric chloride is dark black solid while hydrated salt, FeCl3 . 6H2O is yellowish-
brown deliquescent crystalline solid. Both are soluble in water as well as in ether forming

solvated species, [Fe(H2O)4Cl2]Cl . 2H2O and O FeCl3 respectively..

It is sublimed at 300°C giving a dimeric gas, .

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(b) Chemical : (i) Action of heat :
6H;9#&H09#I
/ G
3

–– 2FeCl3 (anhydrous) 2FeCl2 + Cl2

S

–– 2[FeCl3. 6H2O] Fe2O3 + 6HCl + 9H2O

(ii) As oxidising agent :
w 1(
; J

–– 2FeCl3 + SnCl2 '

(
2FeCl2 + SnCl4 E

–– 2FeCl3 + H2S 2FeCl2 + 2HCl + S

...
- S (ii)
j FeCl + 6NH
3 3
FeCl3
. 6NH3 ; FeCl3 + NOCl FeCl3.NOCl
4. Ferrous-oxide FeO (Black)
Preparation
FeC2O4 In absence of air
FeO + CO + CO2
Properties
It is stable at high temperature and on cooling slowly disproportionates into Fe3O4 and iron.
 5. Ferrous chloride (FeCl2 )
Preparation
heated in
Fe + 2HCl FeCl2 + H2
a current of HCl

Properties
(i) 2FeCl3 + H2 2FeCl2 + 2HCl
(ii) It is deliquescent in air like FeCl3
(iii) It is soluble in water, alcohol.
(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

B. COMPOUND OF ZINC :

1. Zinc oxide, ZnO (Chinese white or philosopher's wool)

It is found in nature as zincite or red zinc ore.
Preparation

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

(b) ZnO is formed when ZnS is oxidised
2ZnS + 3O2 2ZnO + 2SO2

Properties
(a) Physical : It is a white powder which becomes yellow on heating due to change in the structure of lattice
but again turns white on cooling. it is insoluble in water and sublimes at 400°C.
(b) Chemical : It is amphoteric in nature.
ZnO + H2SO4 ZnSO4 + H2O
ZnO + 2NaOH Na2ZnO2 + H2O

Uses
It is used as a white paint. It does not get tarnished even in presence of H2S because ZnS is
also white.

2. Zinc Sulphate, ZnSO4 . 7H2O (White vitriol)

Preparation
(a) Zn + H2SO4 ZnSO4 + H2
(b) ZnO + H2SO4 ZnSO4 + H2O
(c) ZnCO3 + H2SO4 ZnSO4 + H2O + CO2
I#;;.-H
z
Properties &HQ #9H /.k.I#9 .< /&#UH 4* c

(a) Physical : It is a colourless, crystalline solid soluble in water. It slowly effloresces when exposed to air.
It is isomorphous with Epsom salt (MgSO4 . 7H2O)
(b) Chemical : (i) ZnSO4 + 2NaOH Zn(OH)2 (white) + Na2SO4
Zn(OH)2 + 2NaOH Na2ZnO2 (soluble complex) + 2H2O
100 º C 280 º C 800 º C
(ii) ZnSO4.7H2O ZnSO4 . 6H2O ZnSO4 ZnO + SO3
 3. Zinc Chloride ZnCl2.2H2O
Preparation
ZnCl2 . 2H2O Zn(OH)Cl + HCl + H2O
Zn(OH)Cl ZnO + HCl
Hence anhydrous zinc chloride is obtained either by heating zinc in a current of chlorine gas
or by distilling a mixture of zinc powder and mercuric chloride
Zn + Cl2 ZnCl2 ; Zn + HgCl2 ZnCl2 + Hg
Properties
(a) It is a white crystalline solid, deliquescent and soluble in water.
excess
(b) ZnCl2 + NaOH Zn(OH)2n S
Na2[Zn(OH)4]
excess
(c) ZnCl2 + NH4OH Zn(OH)2 ; c
[Zn(NH3)4]2+
x&.;H
C. COMPOUND OF COPPER :
1. Copper Sulphate, CuSO4 . 5H2O (Blue Vitriol)
It is also called 'Nilathotha'.
Preparation
1
(i) Cu + H2SO4 + O CuSO4 + H2O
2 2
(ii) CuCO3.Cu(OH)2 (malachite ore) + 2H2SO4 2CuSO4 + 3H2O + CO2
Properties
(a) Physical : It is a blue crystalline compound and is soluble in water.
w

(b) Chemical : (i) 2CuSO4 + Na2CO3 + H2O Cu(OH)2 (blue) + Na2SO4 + CO2 .
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(ii) 2CuSO4 + 2FeSO4 + 2KI Cu2 I2 + Fe2(SO4)3 + K2SO4

; 1 4
w 1 ( ; 1J 1 w1 S

(iii) 2CuSO4 + 2KSCN + SO2 + 2H2O 2CuSCN (white) + K2SO4 + 2H2SO4

air 100 º C 250 º C

(iv) CuSO4.5H2O CuSO4.4H2O CuSO4 . H2O CuSO4
effloresce s

750 º C
CuO + SO2 + O2
(v) Action of NH4OH : With ammonia solution, it forms the soluble blue complex. First it
forms a precipitate of Cu(OH)2 which dissolves in excess of ammonia solution
CuSO4 + 2NH4OH Cu(OH)2 $ + (NH4)SO4 S

TI:H
Cu(OH)2 + 2NH4OH + (NH4)2SO4 Cu(NH3)4SO4 + 4H2O
s
-4I49 (Tetrammine cupric sulphate)
/4I:TIH TI:H
-4<*H9
The complex is known as Schwitzer's reagent which is used for dissolving cellulose in the
manufacture of artificial silk.
(vi) Action of alkalies : Alkalies form a pale bule precipitate of copper hydroxide.
CuSO4 + 2NaOH Cu(OH)2 + Na2SO4
(vii) Action of potassium iodide : First cupric iodide is formed which decomposes to give
white cuprous iodide and iodine. E
; 1 ( $ $
1
'

w 1 S
'

2CuSO4 + 4KI Cu2I2 + 2K2SO4 + I2

' K 1 E

(viii) Action of H2S : When H2S is pased through copper sulphate solution, a black precipitate
of copper sulphide is formed.
CuSO4 + H2S CuS$ + H2SO4 c

TI#-U
The black precipitate dissolves in conc. HNO3
'
1( ; 1A
$; 1( E

3CuS + 8HNO3 3Cu(NO3)2 + 2NO + 3S + 4H2O

' /4I:TIH
-49H

E
 /
{
'

'

'

,/
c
4 '

4 ' '
'

c
c w X

; (
(ix) Action of sodium thiosulphate etc.
w(</
m
|
'

CuSO4 + Na2S2O3 CuS2O3 + Na2SO4

A#4 AQ 4* ;
'

S
'
2CuS2O3 + Na2S2O3 Cu2S2O3 + Na2S4O6
3Cu2S2O3 + 2Na2S2O3 Na4[Cu6(S2O3)5]
(Sodium cuprothiosulphate)
$

2. Cupric Oxide, CuO

It is called black oxide of copper and is found in nature as tenorite.
Preparation
(i) By heating Cu2O in air or by heating copper for a long time in air (the temperature should
not exceed above 1100°C)
2Cu2O + O2 4CuO
2Cu + O2 2CuO K A#<H #X.<H
(ii) 2Cu(NO3)2 2CuO + 4NO2 + O2
(iii) On a commercial scale, it is obtained by heating/calcination of malachite which is found
in nature.
CuCO3 . Cu(OH)2 2CuO + CO2 + H2O

Properties
(a) Physical : It is black powder insoluble in water and stable to moderate heating.

(b) Chemical : (a) 4CuO 2Cu2O + O2

(b) The oxide is insoluble in water but dissolves in acids forming corresponding salts.
(c) It is reduced to metallic copper by reducing agents like hydrogen, carbon and carbon
monoxide.

3. Cupric Chloride, CuCl2 . 2H2O

Preparation
(i) The metal or cupric oxide or cupric hydroxide or copper carbonate is dissolved in concentrated
HCl. The resulting solution on crystallisation gives green crystals of hydrated cupric chloride.

2Cu + 4HCl + O2 2CuCl2 + 2H2O

CuO + 2HCl CuCl2 + H2O
Cu(OH)2CuCO3 + 4HCl 2CuCl2 + 3H2O + CO2
(ii) Anhydrous cupric chloride is obtained as a dark brown mass when copper metal is heated
in excess of chlorine gas or by heating hydrated cupric chloride in HCl gas at 150°C.
Cu + Cl2 CuCl2 (P S

Properties ! -:-I;X4 )
S L
K

(a) Physical : It is deliquescent compound and is readily soluble in water. The dilute solution is blue but
,; concentrated solution is, however, green. It changes to yellow when concentrated HCl is
! -: %.;94 )

6
L 6
S added. The blue colour is due to complex cation [Cu(H2O)4]2+ and yellow colour due to complex

#:;:k<#I
anion [CuCl4]2– and green when both are present.

(b) Chemical : (i) 2CuCl2 Cu2Cl2 + Cl2

-#:/#
3CuCl2 . 2H2O CuO + Cu2Cl2 + 2HCl + Cl2 + 5H2O Y
Strong
QHII4x
(ii) CuCl2 + Cu Cu2Cl2
2CuCl2 + SO2 + 2H2O Cu2Cl2 + 2HCl + H2SO4
 (iii) A pale blue precipitate of basic cupric chloride CuCl2 . 3Cu(OH)2 is obtained when NaOH
is added. } TI:H
CuCl2 + 2NaOH Cu(OH)2 + 2NaCl
CuCl2 + 3Cu(OH)2 CuCl2 . 3Cu(OH)2 c K TI:H @*;
It dissolves in ammonium hydroxide forming a deep blue solution. On evaporation of this
solution deep blue crystals of tetraammine cupric chloride are obtained.
CuCl2 + 4NH4OH [Cu(NH3)4]Cl2 . H2O + 3H2O /4I:TIH
'
TI:H
-4<*I:a
(iv) It is readily reduced to Cu2Cl2 by copper turnings or SO2 gas, or hydrogen (Nascent–
obtained by the action of HCl on Zn) or SnCl2.
D. COMPOUND OF SILVER :
1. Silver Nitrate, AgNO3 (Lunar caustic)
Preparation
heat
3Ag + 4HNO3 (dilute) 3AgNO3 + NO + 2H2O
Properties
(a) Physical : It is a colourless crystalline compound, soluble in water and alcohol. It melts at 212°C.
(b) Chemical : (i) It possesses powerful corrosive action on organic tissues, which it turns black especially
in presence of light. The blackening is due to finely divided metallic silver, reduced by
organic tissue. It is, therefore, stored in coloured bottles.
(ii) On heating above its melting point, it decomposes to silver nitrite and oxygen.
2AgNO3 2AgNO2 + O2 '

When heated red hot, it gives metallic silver

H 2AgNO3 2Ag + 2NO2 + O2
(iii) Solid AgNO3 absorbs ammonia gas with the formation of an addition compound,
AgNO3. 3NH3 . When NH4OH is added to silver nitrate solution, a brown precipitate of
silver oxide appears which dissolves in excess of ammonia forming a complex salt.
2AgNO3 + 2NH4OH m 3 + H 2O
Ag2O + 2NH4NO T94x/
;H9k.<#I Ag2O + 2NH4NO3 + 2NH4OH 2[Ag(NH3)2]NO3 + 3H2O

#IUQ<H '
(iv) The ammonical solution of AgNO3 react with acetylene to form a white precipitate.
2AgNO3 + 2NH4OH + C2H2 Ag2C2 (silver acetylide) + 2NH4NO3 + 2H2O
(v) Ammonical silver nitrate is called Tollen’s reagent and is used to identify reducing sugars
and aldehydes.

RCHO + 2Ag+ + 3OH– RCOO– + 2Ag + 2H2O

It is known as “silver mirror” test of aldehydes and reducing sugars.
Ag2O + HCHO 2Ag + HCOOH
Ag2O + C6H12O6 2Ag + C6H12O7
e4R
'

$
;
(vi) Reaction with iodine : '
–– 6AgNO3 (excess) + 3I2 + 3H2O AgIO3 + 5AgI + 6HNO3
–– 5AgNO3 + 3I2 (excess) + 3H2O
+
HIO3 + 5AgI+ 5HNO3

2m
$;
d
1 e
;
'

(vii)6AgNO3 + PH3 + 3H2O 6Ag + 6HNO3 + H3PO3 X

'
/

(viii) It dissolves in excess of KCN:

AgNO3 KCN
AgCN KCN K[Ag(CN)2]
white ppt soluble potassium argentocyanide
(ix) AgNO3 gives white precipitate with Na2S2O3; white precipitate changes to black.
2AgNO3 + Na2S2O3 Ag2S2O3 + 2NaNO3
1 (w
white; ppt
Ag2S2O3 S + H2O S
58 ,;
Ag2S + H2SO4
;4
r,;
s black
4&/*x*4<#I.4ic/< =
 2. Silver oxide (Ag2O)
Preparation
It is prepared as brown solid by adding sodium hydroxide solution to silver nitrate solution.
2AgNO3 + 2NaOH Ag2O + 2NaNO3 + H2O

Properties

2Ag2O 4Ag + O2

Photography
light
2AgBr(s) 2Ag + Br2
AgBr + 2Na2S2O3 Na3[Ag(S2O3)2] + NaBr
&Q*4<0:;c.;
Y /4I:;H
E. POTASSIUM PERMANGANATE (KMnO4) : -4<*I:a
Preparation
(a) It is prepared by fusing pyrolusite ore either with KOH or K2CO3 in presence of atmospheric oxygen.
2MnO2 + 4KOH + O2 2K2MnO4 + 2H2O
2MnO2 + 2K2CO3 + O2 2K2MnO4 + 2CO2
The fused mass is extracted with water and the solution is now treated with a current of chlorine or
wb ozone or carbon dioxide to convert manganate into permanganate.
-' K
1
4* $ wg
2K2MnO4 + Cl2 2KMnO4 + 2KCl
^E @
2K2MnO4 + H2O + O3 2KMnO4 + 2KOH + O2
0./*94*#9;.W/-; 3K2MnO4 + 2CO2 2KMnO4 + MnO2 + 2K2CO3
9H#-;.4</ In the laboratory, a manganese(II) ion salt is oxidised by peroxodisulphate to permanganate

E
F
' 2Mn2+ + 5S2O82– + 8H2O 2MnO4– + 10SO42– + 16H+
(b) Electrolytic method :- The potassium manganate solution is taken in an electrolytic cell which contains iron cathode
'
$ $ '
S
'
S
u and nickel
c anode. When current is passed the manganate ion in oxidised to permanganate ion at
,
A anode and hydrogen is liberated at cathode.
' ,
4 4
4
'
'
'

1 / '

4
'

2K+ + MnO42–
,
$ S S
K2MnO4
E 4

At anode : MnO4–2 MnO4– + e–

Green Purple
At cathode : 2H+ + 2e– 2H
2H H2

Properties
(a) Physical : It is purple coloured crystalline compound. It is moderately soluble in water at room temperature.
(b) Chemical : (i) When heated alone or with an alkali, it decomposes evolving oxygen.
wg '

( ;4 ; J u

750 K
2KMnO4 K2MnO4 + MnO2 + O2

4KMnO4 + 4KOH 4K2MnO4 + 2H2O + O2

MnO4 in dilute alkaline, water and acidic solutions is unstable and disproportionates to give
2–

MnO4– and MnO2 . P'g ;Q

;4
3MnO42– + 4H+ 2MnO4– + MnO2 + 2H2O
3MnO42– + 2H2O 2MnO4– + MnO2 + 4OH–
wg

(ii) 2KMnO4 + 3H2SO4 2KHSO4 + (MnO3)2SO4 + 2H2O

wg

(MnO3)2SO4 + H2O Mn2O7 + H2SO4

3
Mn2O7 O 2MnO2 +
2 2
(iii) A mixture of sulphur, charcoal and KMnO4 forms an explosive powder.
 %#
) (iv)
/4 In strongly alkaline medium KMnO is reduced to manganate.
4

2KMnO4 + 2KOH (conc.) 2K2 MnO4 + H2O + [O] Vk<4Q K

V:&<
solution is dilute then K2MnO4 is converted in to MnO2 EQ
2K2MnO4 + 2H2O 2MnO2 + 4KOH + 2[O]
% T ) This type of behaviour is shown by KMnO4 itself in neutral medium
3e– + 2H2O + MnO4– MnO2 + 4OH– V K
< <
EQ C< E

F
(v) Reactions in Acidic Medium
(vi) Oxalates to CO2 pG $
@<<4Q '
S
k<(;
%X-Q
'

%
K
4

(vii) Iodides to Iodine ~ $

'
S
K 1

(viii) Sulphites to sulphates $< /4

, '

/4 ('
' K
S S
'
(ix) It oxidizes H2S to S
(x) It oxidizes SO2 to sulphuric acid
(xi) It oxidizes Nitrites to nitrates "4. K
'

<W
K

(xii) In alkaline medium KMnO

c 4 solution is also known as Bayer’s reagent (1% alkaline KMnO4 solution).

2MnO4– + – + H2O 2MnO2 + O3– + 2OH–

'

$
$W
~ K
'

2MnO4– + 3H2S 2MnO2 + 2OH– +2H2O + 3S pG $; A

K
S n
2MnO4 + 3Mn + 2H2O
– 2+
5MnO2 + 4H C*;
+ ~
K
CQ E<
8MnO4– + 3S2O32– + H2O 8MnO2 + 6SO42– + 2OH–

''QAX
'M
'

@-.0.- (

*
/4
(xiii) 2KMnO4 + 3H2SO4 K2SO4 + 2MnSO4 + 3H2O + 5[O] K
'

K
S S

kH0.:/ c

2MnO4– + 16H+ + 5S2– ' 2Mn2+ + 8H2O + 5S

2MnO4– + 6H+ + 5H2O2 5O2 + Mn2+ + 8H2O. ~
7X4X K EX

[F] POTASSIUM DICHROMATE (K2Cr2O7) :

Preparation
The chromite ore is roasted with sodium carbonate in presence of air in a reverberatory furnace.
; 1 ( ; 1 G 1 +
b P'G
Roasting
4FeO. Cr2O3 (chromite ore) + 8Na2CO3 + 7O2 in air
8Na2CrO4 + 2Fe2O3 + 8CO2
The roasted mass is extracted with water when Na2CrO4 goes into the solution leaving behind insoluble
Fe2O3. The solution is then 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 Na2Cr2O 7 are obtained. Hot saturated solution of Na2Cr2O 7 is then
treated with KCl when orange red crystals of K2Cr2O7 are obtained on crystallisation.
Na2Cr2O7 + 2KCI K2Cr2O7 + 2 NaCl

K2Cr2O7 is preferred over Na2Cr2O7 as a primary standard in volumetric estimation because Na2Cr2O7 is
hygroscopic in nature but K2Cr2O7 is not.

Properties
(a) Physical :
It is orange-red coloured crystalline compound. It is moderately soluble in cold water but freely soluble
in hot water. It melts at 398°C.

(b) Chemical :
(i) Effect of heating : On heating strongly, it decomposes liberating oxygen.
wb ;4 wG 4
W 3
2K2Cr2O7 2K2CrO4 + Cr2O3 + O
] 2 2
 $

On heating with alkalies, it is converted to chromate, i.e., the colour changes from orange to yellow.
On acidifying, yellow colour again changes to orange.
K2Cr2O7 + 2KOH 2K2CrO4 + H2O

m Cr2O 27 + 2OH¯ 2CrO 24 + H2O

Orange Yellow

m 2CrO 24 + 2H+ Cr2O 27 + H2O

Yellow Orange

In alkaline solution, chromate ions are present while in acidic solution, dichromate ions are present.

(ii) K2Cr2O7 + 2H2SO4 (conc. & cold) 2CrO

c
3
(bright orange/red) + 2KHSO4 + H2O

2K2Cr2O7 + 8H2SO4 (conc. & Hot) 2K2SO4 + 8H2O + 2Cr2(SO4)3 + 3O2

(iii) Blue colour in aqueous solution
'
fades away slowly' due to the decomposition
' of CrO 5 to Cr3+ ions
a ' ' '
' <
'
'

andv oxygen. In>less' acidic solution K2Cr 2O 7 and H 2O 2 give

' ' ' ' < salt which is violet coloured
'
v <
v
and
S
S

diamagnetic
$ $ the formation
due to $ g –.
ofI [CrO(O2)(OH)]
$ c

) c

(c) Oxidising properties

The dichromates act as powerful oxidising agent in acidic medium. In presence of dil H2SO4, K2Cr2O7
liberates Nascent oxygen and therefore acts as an oxidising agent.
K2Cr2O7 + 4H2SO4 K2SO4 + Cr2(SO4)3 + 4H2O + 3[O]
In terms of electronic concept the Cr2 O 72 ion takes up electrons in the acidic medium and hence
acts as an oxidising agent.

Cr2 O 27 14 H 6e 2 Cr 3 7H 2 O
(i) It oxidises iodides to iodine ~ $ K $<
c

G ;
#
(ii) Acidified ferrous sulphate to ferric sulphate
, 1 '
1 '
h S
3

(iii) Oxidises H2S to sulphur p) $; A K S A

(iv) It oxidises sulphites to sulphates, chlorides to chlorine, nitrites to nitrates, thiosulphates to sulphates S

and sulphur and stannous (Sn+2 ) salts to stannic (Sn+4 ) salts.

(v) It oxidises SO2 to sulphuric acid.
(vi) Cr2O 27 + 3H2S + 8H+ 2Cr3+ + 7H2O + 3S

$4<.- &#I.0H (vii) K2Cr2O7 + 2C (charcoal) Cr2O3 + K2CO3 + CO 9#;.4</

;&./ ;H/;
-'
W.iH m (viii) Chromyl chloride test : 4Cl– + Cr2O72– + 6H+ 2CrO2Cl2 (deep red) + 3H2O
CrO2Cl2 + 4OH– CrO42– (yellow) + 2Cl– + 2H2O Y
-&94kQI -&I49.0H
CrO42– (yellow) + Pb2+ PbCrO4 (yellow)
'
1 ,
4

$/
(ix) Cr2O72– (concentrated solution) + 2Ag+ Ag2Cr2O7 (reddish brown) #I
'
S S '(
;
Ag2Cr2O7 + H2 O boil Ag2CrO4 + CrO4 + 2H . 2– +
#

4
b '
S

(
V
X- 7 #/ ; $;
u
;
W
4
' V
9 Q Q S
(
I
F/4 Q
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S
S 4
0.H
TI:H

K TI:H -4I49 *#0H

0: ;4
0HH4k9*/4/.;.#< 4* # 4W
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.<;4 #<0 E9 c

V $ ; b $; F •E
K % u( )
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S S X $; ; A7
X 4 S 4
c

S
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F – Block
The inner transition elements (f-block)
The f-block elements comprises of the two series,
A. lanthanoids (the fourteen elements following lanthanum) and
B. actinoids (the fourteen elements following actinum).

A. Lanthanoids (4f - series) :

Electronic configuration
The electronic configurations of all the tripositive ions which is the most stable oxidation state of all the lanthanoids,
are of the form 4fn ( n = 1 to 14 with increasing atomic number)
Atomic sizes
There is decrease in atomic and ionic radii from lanthanum to lutetium due to lanthanoid contraction. The cumula
-tive effect of the contraction of the lanthanoids series, known as lanthanoids contraction, causes the radii of the
members of the third transition series to be very similar to those of the corresponding members of the second
series.
Oxidation state
In the lanthaoids, La(III) and Ln(III) compounds are predominant species. However, occasionally +2 and +4 ions in
solution or in solid compounds are also obtained.
General characteristics
All the lanthanoids are silvery white soft metals and tarnish rapidly in air. The hardness increases with increasing
atomic number, samarium is hard as steel. They have typical metallic structure and are good conductors of heat
and electricity. The lanthanoids ions other than the f° type (La+3 and Ce4+) and the f14 type (Yb2+ and Lu3+) are all
paramagnetic. The paramagnetism rises to maximum in neodyamium.

Uses of lanthanoids
Mixed oxides of lanthanoids are employed as catalyst in petroleum cracking.
B. Actinoids (5f - series) :
The actinoids are radioactive elements.
Electronic configuration
The irregularities in the electronic configuration of the actinoid, like those in the lanthanoids are related to the
stabilities of the f°, f7 and f14 occupancies of the 5f orbitals. Thus the configurations of Am and Cm are [Rn] 5f 7 7s2
and [Rn] 5f76d17s2.
Ionic Sizes
There is a gradual decrease in the size of atoms or M3+ ions across the series. This may be referred to as the
actinoids contraction (like lanthanoids contraction).
Oxidation states
The actinoids show in general +3 oxidation state. The elements, in the first half to the series frequently exhibit
higher oxidation state. e.g. The maximum oxidation state increases from +4 in Th to +5, +6 and +7 respectively in
Pa, U and Np but decreases in succeeding elements.
General characteristics and comparision with Lanthanoids
1. The actinoids metals are all silvery white in appearance but display a variety of structures.
2. The actinoids are highly reactive metals, especially when divided, the action of boiling water on them, for example,
gives a mixture of oxide and hydride and combination with most metals takes place at moderate temperatures;
hydrochloric acid attacks all metals but most are slightly affected by nitric acid owing to the formation of protective
oxide layers; alkalies have no action.

Uses of actinoids
1. Thorium is used in atomic reactors and in the treatment of cancer. Its salts are used in making incandescent
gas mantles.
2. Uranium
3. Plutonium
 Examples
1. On what ground you can say that scandium (Z = 21) is a transition element but zinc (Z = 30) is not?

Sol. On the basis of incompletely filled 3d orbitals of scandium, [Ar]18 3d1 4s2 , and completely filled 3d orbitals of Zn, [Ar]18
3d10 4s2, they are considered transition and non-transition elements respectively.

2. The element with the electronic configuration [Xe]54 4f14 5d1 6s2 is a :
(A) representative element (B) d-block element (C) lanthanoid (D) actinoid

Sol. After achieving 4f14 5d0 6s2 configuration, the next electron goes to 5d and this is the case of Lu(Z = 71) which is the last
element of lanthanoid series. Therefore, (C) option is correct.

3. Why do the transition elements have higher boiling & melting points ?

Sol. Because of having larger number of unpaired electrons in their atoms, they have stronger interatomic interaction and
hence stronger bonding between atoms. Hence strong metallic bonds between the atoms of these elements attribute to
their high melting and boiling points.

4. Explain the blue colour of CuSO4.5H2O.

Sol. Cu2+ ion (3d9) absorbs red light from the visible region, for the promotion of 3d electrons, the ions reflect blue light and
appear blue.

5. Determine the magnetic moment of a divalent ion in aqueous solution if its atomic number is 25.

Sol. The metal having atomic number 25 has electron configuration [Ar]18 3d5 4s2. So its divalent ion in aqueous solution will
have electron configuration [Ar]18 3d5 4s0. Thus it has five unpaired electrons.

So (spin)
= 5(5 2) = 5.92 BM.

6. How iron (III) catalyses the reaction between iodide & persulphate?

Sol. 2Fe3+ + 2 – 2Fe2+ + 2

2Fe2+ + S2O82– 2Fe3+ + 2SO42–
________________________________________________________

Fe ( )
2 – + S2O82– 2
+ 2 SO42–

7. Zn (OH)2 [X].
Select the correct statement (s) for the compound X.
(A) X on heating with cobalt nitrate gives green mass
(B) X on heating alone, becomes yellow but turns white on cooling.
(C) Solution of X in dilute HCl gives bluish white/white precipitate with excess potassium ferrocyanide.
(D) X is insoluble in aqueous sodium hydroxide.

Sol. (A) X is ZnO which on heating with cobalt nitrate gives ZnO. CoO, the Rinmann's green.
(B) It turns yellow on heating and becomes white on cooling.
(C) ZnCl2 forms bluish white/white precipitate. Zn3K2[Fe(CN)6]2.
3 Zn2+ + 2 K+ + 2 [Fe(CN)6]4– K2Zn3[Fe(CN)6]2
(D) ZnO + 2NaOH Na2ZnO2 (soluble complex) + H2O.
So options A, B & C are correct and (D) is incorrect.
8. Anhydrous white solid (A) on addition of potassium iodide solution gave a brown precipitate which turned white (B) on
addition of excess of hypo solution. When potassium cyanide is added to an aqueous solution of (A) a white precipitate
is formed which then dissolves in excess forming (C). A solution (1%) of (A) on adding to a solution of white portion of egg
produced violet colouration in alkaline medium (i.e. in presence of NaOH). Identify compound (A) and explain the reactions.

Sol. As 1% solution of (A) produced violet colouration with white portion of egg (Biuret test) and (A) with potassium iodide
gives brown precipitate which turned white on adding hypo. The (A) may be anhydrous CuSO 4 (White). This is further
confirmed by the reaction of (A) with potassium cyanide.
2CuSO4 + 4K Cu2 2 (white) + 2 (yellow or brown) + 2K2SO4
(A) (B)
2
+ 2Na S O
2 2 3
Na S O
2 4 6
+ 2Na
2CuSO4 + 4KCN 2 Cu(CN)2 (yellow) + 2K2SO4 ; 2Cu(CN)2 2CuCN (white) + (CN)2
2CuCN + 6 KCN 2 K3 [Cu(CN)4] (colourless soluble complex).
(C)

100 º C 250 º C
9. CuSO4.5H2O [X] (s) [Y] (s)
(A) X and Y are CuSO4. 3H2O and CuSO4 (B) X and Y are CuSO4. 3H2O and CuSO4 . H2O
(C) X and Y are CuSO4. H2O and CuSO4 (D) X and Y are CuSO4 and CuO

100 º C 250 º C
Sol. CuSO4.5H2O CuSO4.H2O(s) CuSO4 (s).
So, (C) option is correct.

10. An inorganic compound (A) has garnet red prismatic crystals. (A) is moderately soluble in water and dissolves in cold
concentrated H2SO4 to yield red crystals (B). In presence of dilute H2SO4 it converts a pungent gas (C) into a yellow
turbidity (D) and converts a suffocating gas (E) into a green solution (F). The gas (C) and (E) also combine to produce the
yellow turbidity (D). With K and starch in presence of dilute. H2SO4 (A) yields blue colour. (A) and concentrated H2SO4
mixture is used as a cleansing agent for glassware in the laboratory. Identify (A) and explain the reactions.

Sol. As compound (A) has garnet red prismatic crystals which with cold conc. H2SO4 gives red crystals and a suffocating gas
(SO2) turns its solution in water in to green coloured solution, therefore compound (A) may be K2Cr2O7 .
K2Cr2O7 + 4H2SO4 + 3H2S KHSO4 + 2 CrO3 (red crystals) + H2O
(A) (B)
K2Cr2O7 + 4H2SO4 + 3H2S K2SO4 + Cr2 (SO4)3 + 7H2O + 3S (Yellow)
(C) (D)
K2Cr2O7 + H2SO4 + 3SO2 Cr2 (SO4)3 (Green solution) + K2SO4 + H2O
(E) (F)
K2Cr2O7 + 7H2SO4 + 6K 4K2SO4 + Cr2 (SO4)3 + 7H2O + 3 2

2
+ Starch Blue colour

11. The chemistry of the actinoid elements is not so smooth as that of the lanthanoid. Justify this statement by giving some
examples from the oxidation state of these elements.

Sol. Lanthanoids show limited number of oxidation state, viz, +2, +3 and +4 (out of which +3 is most common). This is
because of large energy gap between 4f, 5d and 6s subshells, the dominant oxidation state of actinoids is also + 3 but
they show a number of other oxidation states also, e.g. uranium (Z = 92) and plutonium (Z = 94), show +3 +4 +5 and +6
neptunium (Z = 94) shows +3 +4 +5 and +7 etc. This is due to small energy difference between 5f, 6d and 7s subshell of
the actinoids
12. A compound (A) is used in paints instead of salts of lead. Compound (A) is obtained when a white compound (B) is
strongly heated. Compound (B) is insoluble in water but dissolves in sodium hydroxide forming a solution of compound
(C). The compound (A) on heating with coke gives a metal (D) and a gas (E) which burns with blue flame. (B) also
dissolves in ammonium sulphate solution mixed with ammonium hydroxide. Solution of compound (A) in dilute HCl gives
a bluish white / white precipitate (F) with excess of K4[Fe(CN)6]. Identify (A) to (F) and explain the reactions.

Ans. (A) ZnO, (B) Zn(OH)2, (C) Na2 ZnO2 , (D) Zn, (E) CO, (F) K2Zn3 [Fe(CN)6]2

Sol. Zn(OH)2 (B) ZnO (A) + H2O.

Zn(OH)2 (B) + 2OH– [Zn(OH)4]2– (C) (soluble complex).

ZnO (A) + C Zn (D) + CO (E).

Zn(OH)2 (B) + 4NH3 [Zn(NH3)4]2+ (soluble complex) + 2OH–.
ZnO + 2HCl ZnCl2 + H2O.
3ZnCl2 + 2K4[Fe(CN)6] K2Zn3[Fe(CN)6]2 (bluish white/white) (F) + 6KCl.

13. An unknown inorganic compound (X) gave the following reactions:

(i) The compound (X) on heating gave a residue, oxygen and oxide of nitrogen.
(ii) An aqueous solution of compound (X) on addition to tap water gave a turbidity which did not dissolve in HNO 3.
(iii) The turbidity dissolves in NH4OH.
Identify the compound (X) and give equations for the reactions (i), (ii) & (iii).

Ans. X = AgNO3

Sol. 2AgNO3 (X) 2 Ag + 2NO2 + O2 .

AgNO3 (aq.) + Cl —
AgCl (white) + NO3— .
AgCl + 2NH3 [Ag(NH3)2]+ (soluble complex).

14. Amongst [TiF6]2– , [CoF6]3– , Cu2 Cl2 and [NiCl4]2– [Atomic number ; Ti = 22, Co = 27, Cu = 29, Ni = 28] the colourless
species are :
(A) [TiF6]2– and [Cu2Cl2] (B) Cu2Cl2 and [NiCl4]2– (C) [TiF6]2– and [CoF6]3– (D) [CoF6]3– and [NiCl4]2–

Ans. (A)

Sol. In [TiF6]2– the titanium is in +4 oxidation state having the electronic configuration [Ar]18 3d0 4s0. Similarly in Cu2Cl2 the
copper is in +1 oxidation state having the electronic configuration [Ar]18 3d10 4s0. As they do not have any unpaired
electrons for d-d transition, they are therefore colourless.
In [NiCl4]2– the nickel is in +2 oxidation state and electronic configuration is [Ar]18 3d8 4s0. As it has two unpaired
electrons, so the complex is coloured.
In [CoF6]3–, the cobalt is in +3 oxidation state having electron configuration [Ar] 3d6 4s0. As it has four unpaired electrons,
so the complex is coloured.

15. Match the reactions given in column-I with the characteristic(s) of the reaction products given in column-II.
Column-I Column-II
Zn
(A) TiCl4 (p) One of the products is bright orange coloured but diamagnetic.

573 K
(B) FeCl3 (q) One of the products is green coloured and paramagnetic.
750 K
(C) KMnO4 (r) One of the products is violet and paramagnetic.
(D) K2Cr2O7 + H2SO4 (cold & conc.) (s) One of the products exists as dimer.

Ans. [A – r] ; [B – s ; [C – q] ; [D – p].
 Zn
Sol. (A) TiCl4 TiCl3, violet (one unpaired electron so d-d transition is possible).

573 K
(B) 2FeCl3 gas dimer..

750 K
(C) 2KMnO4 K2MnO4 green (one unpaired electron so d-d transition is possible) + MnO 2 + O2 .

(D) K2Cr2O7 + 2H2SO4 2CrO3 bright orange (diamagnetic) + 2KHSO4 + H2O.

16. Which of the following is true for the species having 3d4 configuration ?
(A) Cr2+ is reducing in nature. (B) Mn3+ is oxidising in nature.
(C) Both (A) and (B) (D) None of these
Sol. Cr2+ is reducing as its configuration changes from d4 to d3, the latter having a half-filled t32g energy level of 3d orbitals in
octahedral crystal field spliting. On the other hand, the change from Mn3+ to Mn2+ results in the half-filled (d5) configuration
which has extra stability.
Therefore, (C) option is correct.
17. Which of the following increasing order of oxidising power is correct for the following species ?
VO2+ , MnO4– , Cr2O72–
(A) VO2+ < Cr2O72– < MnO4– (B) VO2+ < MnO4– < Cr2O72–
(C) Cr2O72– < VO2+ < MnO4– (D) Cr2O72– < MnO4– < VO2+
Sol. This is attributed to the increasing stability of the lower species to which they are reduced.
MnO4– is reduced to Mn2+ which has stable half filled valence shell electron configuration [3d5].
Cr2O72– is reduced to Cr3+ which has half filled t32g energy level of 3d orbitals in octahedral crystal field spliting
VO2+ is reduced to V3+ which has electronic configuration [Ar]18 3d2 4s0.
So the order of increasing stability of the reduced species is Mn2+ > Cr3+ > V3+ and, therefore, the increasing order of
oxidising power is VO2+ < Cr2O72– < MnO4– .
Therefore, (A) option is correct.
18. Which of the following statement(s) is/are correct ?
(A) Transition metals and many of their compounds show paramagnetic behaviour.
(B) The enthalpies of atomisation of the transition metals are high
(C) The transition metals generally form coloured compounds
(D) Transition metals and their many compounds act as good catalyst.
Sol. (A) As metal ions generally contain one or more unpaired electrons in them & hence their complexes are generally
paramagnetic
(B) Because of having larger number of unpaired electrons in their atoms, they have stronger inter atomic interaction and
hence stronger bonding between the atoms.
(C) According to CFT, in presence of ligands the colour of the compound is due to the d-d transition of the electrons.
(D) This activity is ascribed to their ability to adopt multiple oxidation state and to form complexes.
Therefore, (A,B,C,D) options are correct.
19. When CO2 is passed into aqueous :
(A) Na2CrO4 solution, its yellow colour changes to orange.
(B) K2MnO4 solution, it disproportionates to KMnO4 and MnO2
(C) Na2Cr2O7 solution, its orange colour changes to green
(D) KMnO4 solution, its pink colour changes to green.

H
Sol. (A) Na2CrO4 Na2Cr2O7 (orange colour)
H
(B) MnO42– MnO4– + MnO2 , in neutral or acidic medium
(C) False - In acidic medium no colour change takes place.
–
OH
(D) MnO4– + e– MnO42– ; in strong alkaline medium pink colour of KMnO4 changes to green.
Therefore, (A,B) options are correct.
20. Which of the following statement(s) is (are) not correct with reference to ferrous and ferric ions
(A) Fe3+ gives brown colour with potassium ferricyanide
(B) Fe2+ gives blue precipitate with potassium ferricyanide
(C) Fe3+ gives red colour with potassium sulphocyanide
(D) Fe2+ gives brown colour with potassium sulphocyanide

Sol. Fe3+ produces red colouration with KSCN but Fe2+ does not give brown colour with KSCN.
Therefore, (D) option is correct.

21. Match the reactions in Column I with nature of the reactions/type of the products in Column II.
Column I Column II
(A) AgNO3(aq) + I2 (excess) + H2O (p) Disproportionation
(B) K2MnO4(aq) + CO2(g) (q) Comproportionation

(C) Na2Cr2O7 + C (r) Redox

(D) CuCl2(aq) + Cu(s) (s) One of the products is insoluble in water

Ans. (A p, r, s) ; (B p, r, s) ; (C r, s) : (D q, r, s)

0 V –1
Sol. (A) 5AgNO3(aq) + 3 I 2 (excess) + 3H2O HIO3 + 5AgI + 5HNO3
So it is redox and disproportionation reaction. AgI insoluble in water.
VI VII IV
(B) 3K 2MnO 4 (aq) + 2CO2(g) 2KMnO 4 + MnO 2 + 2K2CO3
So it is redox and disproportionation reaction. MnO2 insoluble in water.
0 VI III IV II
(C) 2C + Na 2Cr2O 7 Cr2O3 + Na 2CO 3 + CO
So it is redox reaction. Cr2O3 (green pigment) is insoluble in water.
II 0 I
(D) CuCl2 (aq) + Cu (s) Cu2Cl2 (s)
So it is redox and comproportionation reaction. Cu2Cl2 is insoluble in water.