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CHEMISTRY
Transition Elementss
(d-Block Elements)
INTRODUCTION:
Four series of elements are formed by filling the 3d, 4d, 5d and 6d subshells of electrons. Collectively these
comprise the d-block elements. They are often called as transition elements because their position in
periodic table is between the s-block and p-block elements. Their properties are transitional between the
highly reactive metallic elements of s-block (which form ionic compounds) and the elements of p-block
(which are largely covalent). Typically the transition elements have an incompletely filled d level. Atransition
element may be defined as the element whose atom in ground state or ion in one of common oxidation
states, has partly filled d-sub shell i.e. having electrons between 1 to 9.
Group 12 (the zinc group) elements have completely filled d-orbitals in the ground state as well as in their
common oxidation states. Therefore, they are not regarded as transition elements.
The general electronic configuration of d-block elements is (n1) d
110
ns
12
, where n is the outer most shell.
However, palladium does not followthis general electronic configuration. It has electron configuration [Kr]
36
4d
10
5s
0
in order to have stability.
I
st
transition series or 3d series corresponding to filling of 3d sub-shell consists of the following
10 elements of 4
th
period.
21
Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and
30
Zn.
II
nd
transition series or 4d series corresponding to filling of 4d sub-shell consists of the following
10 elements of 5
th
period.
39
Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag and
48
Cd.
III
rd
transition series or 5d series corresponding to filling of 5d sub-shell consists of following
10 elements of 6
th
period.
57
La,
72
Hf, Ta, W, Re, Os, Ir, Pt, Au and
80
Hg.
IV
th
transition series or 6d series corresponding to the filling of 6d sub-shell starts with
89
Ac followed
by elements with atomic number 104 onwards.
There are greater horizontal similarities in the properties of the transition elements. However, some
group similarities also exist.
Example-1 On what ground you can say that scandium (Z = 21) is a transition element but zinc (Z = 30) is not?
Solution On the basis of incompletely filled 3d orbitals of scandium, [Ar]
18
3d
1
4s
2
, and completely filled 3d
orbitals of Zn, [Ar]
18
3d
10
4s
2
, they are considered transition and non-transition elements respectively.
Example-2 The element with the electronic configuration [Xe]
54
4f
14
5d
1
6s
2
is a :
(A) representative element (B) d-block element
(C) lanthanoid (D) actinoid
Solution After achieving 4f
14
5d
0
6s
2
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.
Example-3 The number of transition series is :
(A) two (B) three (C) four (D) five
Solution There are four transition series ; 3d, 4d, 5d and 6d series.
Therefore, (C) option is correct.
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CHEMISTRY
GENERAL TRENDS IN THE CHEMISTRY OF TRANSITION ELEMENTS.
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.
Lattice Structures of Transition Metals (Table-1)
Sc Ti V Cr Mn Fe Co Ni Cu Zn
hcp hcp bcc bcc X bcc ccp ccp ccp X
(bcc) (bcc) (bcc,ccp) (hcp) (hcp) (hcp)
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Hcp hcp bcc bcc hcp hcp ccp ccp ccp X
(bcc) (bcc) (hcp)
La Hf Ta W Re Os Ir Pt Au Hg
hcp hcp bcc bcc hcp hcp ccp ccp ccp X
(ccp, bcc) (bcc)
bcc = body centred cubic ; hcp = hexagonal close packed
ccp = cubic close packed ; X = a typical metal structure
The transition elements (with the exception of copper) are very much hard and have lowvolatility.
They have high enthalpies of atomisation which are shown in figure given below. The maxima at about the
middle of each 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 maximumenthalpies of atomization.
Hence the metals with very high enthalpy of atomisation (i.e., very high boiling point) tend to be noble in their
reactions.
Themetals of thesecond, 4dandthird, 5dseries have greater enthalpies of atomisation thanthecorresponding
elements of the first series, 3d and this is an important factor indicating for the occurrence of much more
frequent metal-metal bonding in compounds of the heavy transition metals.
Graph showing Trends in enthalpies of atomisation of transition elements
Size of atoms and ions :
The atomic radii of the transition metals lie in-between those of s- and p-block elements. The covalent radii
of the elements decreases from left to right across a rowin the transition series, until near the end when the
size increases slightly. The decrease in size is small after mid way. In the beginning, the atomic radius
decreases with the increase in nuclear charge (as atomic number increases), where as the shielding effect
of d-electrons is small. After mid way as the electrons enters the last but one shell, the added d-electron
shields the outer most electrons. Hence with the increase in the d-electrons screening effect increases. This
counter balances the increased nuclear charge. As a result, the atomic radii remain practically same after
chromium.
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CHEMISTRY
Near the end of the series, the increased electron repulsions between the added electrons in the same
orbitals are greater than the attractive forces. This results in the expansion of the electron cloud and thus
atomic radius increases.
The atomic radii, in general, increase down the group. The atomic radii of second series are larger than those
of first transition series. In the atoms of the second transition series, the number of shells are more than
those of the Ist transition series. As a result, the atoms of IInd transition series are larger than those of the
elements of the first transition series. But the atomic radii of the second and third transition series are almost
the same.
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 which essentially compensates for the expected increase in atomic size with
increasing atomic number. The net result of the lanthanoid contraction is that the second and the third
d-series exhibit similar radii (e.g., Zr 160 pm, Hf 159 pm) and have very similar physical and chemical
properties much more than that expected on the basis of usual family relationship.
The trend followed by the ionic radii is same as that followed by atomic radii.
The ionic radii of transition metals are different in different oxidation states.
Melting and boiling points :
The melting and boiling points of the transition series elements are generally very high. The melting points of
the transition elements rise to a maximum and then fall as the atomic number increases. Manganese and
technetiumhave abnormally lowmelting 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 d
5
. After chromium, the number of unpaired
electrons goes ondecreasing. Accordingly, the meltingpoints 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 4s
2
). Due to this stable electronic configuration, the delocalisation of electrons may be
less and thus the metallic bond is much weaker than preceding elements.
Example-4 Why do the transition elements have higher boiling & melting points ?
Solution Because of havinglarger 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.
Example-5 The atomic radii of transition elements in a period are
(A) smaller than those of s-block as well as p-block elements.
(B) larger than those of s-block as well as p-block elements.
(C) smaller than those of s-block but larger than those of p-block elements.
(D) larger than those of s-block but smaller than those of p-block elements.
Solution Across the period the atomic radii generally decrease with increasing atomic number as effective
nuclear charge increase.
Therefore, (C) option is correct.
Density :
The atomic volumes of the transition elements are lowcompared with the elements of group 1 and 2. This is
because the increased nuclear charge is poorly screened and so attracts all the electrons more strongly. In
addition, the extra electrons added occupy inner orbitals. Consequently the densities of the transition metals
are high. The densities of the second row are high and third row values are even higher. Elements with the
highest densities are osmium 22.57 g cm
3
and irridium 22.61 g cm
3
.
Across a period from left to right atomic volumes decrease and atomic masses increase. Hence the
densities also increase across a period.
The last element zinc is an exception, having large atomic volume and hence lower density.
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CHEMISTRY
Ionisation energies or Ionisation enthalpies :
The first ionisation energies of d-block elements are intermediate between those of the s- and p-
blocks. This suggests that the transition elements are less electropositive than groups 1 and 2 and
may form either ionic or covalent bonds depending on the conditions. Generally, the lower valent
states are ionic and the higher valent states are covalent. Across a period fromleft to right ionisation
energies gradually increase with increase in atomic number. This is because the nuclear charge
increases and the atomic size decreases with increase in atomic number along the period.
Consequently making the removal of outer electron difficult.
In a given series, 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.
The effect of increased nuclear charge and screening effect of the added d-electrons tend to oppose
each other. Hence due to these two counter effects, the difference in the ionisation energies of two
successive transition elements is very small on moving across a period.
The first ionisation energy of Zn, Cd, and Hg are very high because of their fully filled (n1) d
10
ns
2
configuration.
II
nd
and III
rd
ionisation energies also increase along a period.
II
nd
ionisation energy of Cr > Mn and Cu > Zn
This is because after the removal of I
st
electron Cr and Cu acquire stable configurations (d
5
&d
10
) and
the removal of II
nd
electron thus become very difficult.
Similarly the IE
2
of
23
V <
24
Cr >
25
Mn and
28
Ni <
29
Cu >
30
Zn
The third ionization energy of Mn is very high because the third electron has to be removed from the stable
half-filled 3d orbital.
The first ionisation energies of the 5d elements are higher as compared to those of 3d and 4d
elements. This is because the weak shielding of nucleus by 4f electrons in 5d elements results in
higher effective nuclear charge acting on the outer valence electrons.
Graph Showing Trends in Ionisation Energies
Example-6 Zn forms only Zn
2+
and not Zn
3+
, why?
Solution In the formation of Zn
3+
, an electron from the d
10
configuration has to be removed which requires
abnormally higher amount of energy.
Oxidation states :
The transition metals exhibit a large number of oxidation states. With the exception of a fewelements, most
of these show variable oxidation states. These different oxidation states are related to the electronic
configuration of their atoms.
The existence of the transition elements in different oxidation states means that their atoms can lose different
number of electrons. 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. For example, scandium
has the outer electronic configuration 3d
1
4s
2
. It exhibits an oxidation state of +2 when it uses both of its
4s-electrons for bonding but it can also show oxidation state of +3 when it uses its two s-electrons and one
d-electron. Similarly, the other atoms can show oxidation states equal to ns-and (n 1) d-electrons.
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CHEMISTRY
Table-2 : Different oxidation states of first transition series.
Element
Outer
electronic
configuration
Oxidation states
Sc
3d
1
4s
2
+3
Ti
3d
2
4s
2
+2, +3, +4
V
3d
3
4s
2
+2, +3, +4, +5
Cr
3d
5
4s
1
+2, +3, (+4), (+5), +6
Mn
3d
5
4s
2
+2, +3, +4, (+5), +6, +7
Fe
3d
6
4s
2
+2, +3, (+4), (+5), (+6)
Co
3d
7
4s
2
+2, +3, (+4)
Ni
3d
8
4s
2
+2, +3, +4
Cu
3d
10
4s
1
+1, +2
Zn
3d
10
4s
2
+2
Oxidation states given in parenthesis are unstable.
Table-3 :Different oxidation states of elements of second transition series.
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
+3 (+3) (+2) +2 +2 +2 +2 +2 +1 +2
+4 (+3) +3 (+4) +3 +3 (+3) (+2)
(+4) +4 (+5) +4 +4 +4 (+3)
+5 +5 (+5) (+6)
+6 (+6)
(+7)
(+8)
Table-4 : Different oxidation states of elements of third transition series.
La Hf Ta W Re Os Ir Pt Au Hg
+3 (+3) (+2) +2 (-1) +2 +2 +2 +1 +1
+4 (+3) (+3) (+1) +3 +3 (+3) +3 +2
(+4) +4 (+2) +4 +4 +4
+5 +5 +3 +6 (+6) (+5)
+6 +4 +8 (+6)
+5
(+6)
+7
It may be noted that the stability of a given oxidation state depends upon the nature of the elements with
which the metal is combined. The highest oxidation states are found in compounds of fluorides and oxides
because fluorine and oxygen are most electronegative elements.
The examination of the common oxidation states exhibited by different transition metals reveals the following
facts :
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CHEMISTRY
(i) The variable oxidation states of transition metals are due to participation of inner (n 1)d and outer ns-
electrons. The lowest oxidation state corresponds to the number of ns-electrons. For example, in the first
transition series, the lowest oxidation states of Cr (3d
5
4s
1
) and Cu(3d
10
4s
1
) are +1 while for others, it is +2
(3d
1 10
4s
2
).
(ii) 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.
(iii) The elements which show the greater number of oxidation states occur in or near the middle of the series.
For example, in the first transition series, manganese exhibits all the oxidation states from +2 to +7. The
lesser number of oxidation states in the beginning of series can be due to the presence of smaller number of
electrons to lose or share (Sc, Ti). On the other hand, at the extreme right hand side end (Cu, Zn), lesser
number of oxidation state is due to large number of d electrons so that only a fewer orbitals are available in
which the electron can share with other for higher valence. The highest oxidation state shown by any transition
metal is +8.
(iv) In the +2 and +3 oxidation states, the bonds formed are mostly ionic. In the compounds of higher oxidation
states (generally formed with oxygen and fluorine), the bonds are essentially covalent. Thus, the bonds in +2
and +3 oxidation states are generally formed by the loss of two or three electrons respectively while the
bonds in higher oxidation states are formed by sharing of d-electrons. For example, in MnO
4

(Mn in +7 state)
all the bonds are covalent.
(v) 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 rutheniumand osmiumin the same group formcompounds
in the +4, +6 and +8 oxidation states.
(vi) Transition metals also form compounds in lowoxidation states such as +1 and 0 or negative. The common
examples are [Ni(CO)
4
], [Fe(CO)
5
] in which nickel and iron are in zero oxidation state.
(vii) The variability of oxidation states in transition elements arises because of incomplete filling of the d-orbitals
in such a way that their oxidation states differ by unity such as V
II
, V
III
, V
IV
and V
V
. This behaviour is in
contrast with the variability of oxidation states of non-transition elements (p-block elements), where oxidation
states normally differ by a unit of two such as Sn
2+
, Sn
4+
, In
+
, In
3+
, etc.
(viii) Unlike p-block elements where the lower oxidation states are favoured by heavier members (due to inert pair
effect), the higher oxidation states are more stable in heavier transition elements. For example, in group 6,
Mo (VI) and W (VI) are found to be more stable than Cr (VI). Therefore, Cr (VI) in the form of dichromate in
acidic medium is a strong oxidising agent whereas MoO
3
and WO
3
are not.
Standard electrode potentials :
The magnitude of ionization enthalpy gives the amount of energy required to remove electrons to form a
particular oxidation state of themetal in a compound. Thus, the valueof ionisation enthalpies gives information
regarding the thermodynamic stability of the transition metal compounds in different oxidation states. Smaller
theionisation enthalpy of the metal, the stableis its compound. For example, the first four ionisationenthalpies
of nickel and platinum are given below:
Table-5 :
Ionisation
enthalpies
Ni Pt
IE
1
+ IE
2 2.49 10
3
kJ mol
1
2.66 10
3
kJ mol
1
IE
3
+ IE
4 8.80 10
3
kJ mol
1
6.70 10
3
kJ mol
1
Total 11.29 10
3
kJ mol
1
9.36 10
3
kJ mol
1
It is clear form the above table that the sum of first two ionization enthalpies is less for nickel than for
platinum.
Ni

Ni
2+
+ 2e

I.E. = 2.49 10
3
kJ mol
1
Pt

Pt
2+
+ 2e

I.E. = 2.66 10
3
kJ mol
1
Therefore, ionization of nickel to Ni
2+
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

Ni
4+
+ 2e

I.E. = 11.29 10
3
kJ mol
1
Pt

Pt
4+
+ 2e

I.E. = 9.36 10
3
kJ mol
1
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CHEMISTRY
Thus, the platinum(IV) compounds are relatively more stable than nickel (IV) compounds. Therefore, K
2
PtCl
6
[having Pt (IV)] is a well-known compound whereas the corresponding nickel compound is not known.
However, in solutions the stability of the compounds depends upon electrode potentials.
Electrode potentials :
In addition to ionisation enthalpy, the other factors such as enthalpy of sublimation, hydration enthalpy,
ionisation enthalpy etc. determine the stability of a particular oxidation state in solution. This can be explained
in terms of their electrode potential values. The oxidation potential of a metal involves the following process:
M(s) M
+
(aq) + e

This process actually takes place in the following three steps as given in following flowchart :
(i) In the first step, the atoms get isolated fromone another and become independent in the gaseous state. This
converts solid metal tothegaseous state. Theenergy needed for this step is knownas enthalpy of sublimation.
M(s) M
+
(g) Enthalpy of sublimation, A
sub
H
O
(ii) In the second step, the outer electron is removed from the isolated atom. The energy required for this change
is ionisation enthalpy.
M(s) M
+
(g) + e

Ionisation enthalpy, IE
(iii) In the third step the gaseous ion gets hydrated. In this process, energy known as hydration enthalpy, is
liberated.
M
+
(g) + nH
2
O M
+
(aq) Enthalpy of hydration, A
hyd
H
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
AH = A
sub
H
O
+ IE + A
hyd
H
Thus, AH gives the enthalpy change required to bring the solid metal, M to the monovalent ion in aqueous
medium, M
+
(aq). An exactly similar cycle may be constructed for the formation of an anion in solution
except that the ionization enthalpy may be replaced by electron gain enthalpy when the gaseous atomgoes
to gaseous anion. AH helps to predict the stability of a particular oxidation state. The smaller the values of
total energy change for a particular oxidation state in aqueous solution, greater will be the stability of that
oxidation state. The electrode potentials are a measure of total energy change. Qualitative, the stability of
the transition metal ions in different oxidation states can be determined on the basis of electrode potential
data. The lower the electrode potential i.e., more negative the standard reduction potential of the electrode,
the more stable is the oxidation state of the transition metal in the aqueous solution.
The electrode potentials of different metals can also be measured by forming the cell with standard hydrogen
electrode. For the measurement of electrode potential of M
2+
| 1M, the e.m.f. of the cell in which the following
reaction occurs is measured :
2H
+
(aq) + M(s) M
2+
(aq) + H
2
(g)
Knowing the potential of 2H
+
(aq) | H
2
(g), it is possible to determine the potential of M
2+
(aq) | M. For the first
transition series, the E
O
values of M
2+
(aq) | Mare given below :
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CHEMISTRY
The observed values of E
O
and those calculated using the data are compared in the following figure.
Thermochemical data (kJ mol
1
) for the first row Transition Elements and the Standard Electrode
potentials for the Reduction of M
II
to M
Table-6 :
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
469
515
398
279
418
427
431
339
130
661
648
653
716
762
757
736
745
908
1310
1370
1590
1510
1560
1640
1750
1960
1730
-1866
-1895
-1925
-1862
-1998
-2079
-2121
-2121
-2059
-1.63
-1.18
-0.90
-1.18
-0.44
-0.28
-0.25
0.34
-0.76
Element (M) Hq (M) H (M ) E /V
a hyd
A
2+ u
A
u u
A
1 f
H
u
A
2 1
H
The results lead to the following conclusions :
(i) There is no regular trend in these values. This is attributed to the irregular variation of ionisation enthalpies
(IE
1
+ IE
2
) and the sublimation energies in the period.
(ii) It may be noted that the electrode potentials of transition metals are lowin comparison to elements of group
2 (e.g., Ca = 2.87 V). Compared to group 2 elements, the transition elements have fairly large ionisation
enthalpies and very large enthalpies of atomisation. These reduce their electrode potentials though their
hydration enthalpies are large.
(iii) Zinc has lowenthalpy of atomisation and fairly large hydration energy. But it has also lowelectrode potential
(0.76 V) because of its very high ionisation enthalpy (IE
1
+ IE
2
).
(iv) It is clear fromabove table and figure that copper has positive reduction potential, E
O
(0.34 V) and this shows
that copper is least reactive metal out of the first transition series. This unique behaviour (+ve) E value of
copper) also accounts for its inability to liberate H
2
fromacids. It has been observed that only oxidizing acids
(such as nitric acid and hot concentrated sulphuric acid) react with copper in which the acids are reduced.
The high energy required to convert Cu(s) to Cu
2+
(aq) is not balanced by its hydration enthalpy.
(v) In general, the value becomes, less negative across the series. This is related to the general increase in the
sum of first and second ionisation enthalpies. It is interesting to note that the values of E of Mn, Ni and Zn
are more negative than expected fromthe general trend. The relatively more negative values of E
O
for Mn and
Zn are due to stability of half filled d-sub-shell in Mn
2+
(3d
5
) and the completely filled (3d
10
) configuration in
Zn
2+
. The exceptionally high E
O
value of Ni from regular trend is related to the highest negative enthalpy of
hydration of Ni
2+
ion.
Trends in the M
3+
| M
2+
Standard Electrode Potentials
Except copper and zinc, all other elements of first transition series show+3 oxidation states also to formM
3+
ions in aqueous solutions. The standard reduction potentials for M
3+
| M
2+
redox couple are given below :
Table-7 :
Ti V Cr Mn Fe Co
E
O
(M
3+
(aq) | M
2+
(aq)
(in Volt)
0.37 0.26 0.41 +1.57 +0.77 +1.97
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These values reveal the following facts :
(i) The low value of scandium reflects the stability of Sc
3+
which has a noble gas configuration.
(ii) The comparatively high value for Mn shows that Mn
2+
(d
5
configuration) is particularly stable. On the other
hand comparatively lowvalue for Fe shows the extra stability of Fe
3+
(d
5
configuration).
(iii) The comparatively low value of V is related to the stability of V
2+
(due to half filled t
2g
3
energy level of 3d
orbitals in octahedral crystal field spitting).
(iv) The E
O
value for Mn
3+
/Mn
2+
couple much more positive than for Cr
3+
/Cr
2+
or Fe
3+
/Fe
2+
. This is because of the
much larger III
rd
ionisation energy of Mn (removal of electron fromd
5
configuration).
Trends in Stability of Higher Oxidation States
Standardelectrode potential data providevaluable information about thestabilities of different oxidation states
shown by an element. The highest oxidation states are shown generally among halides and oxides.
1. In metal halides. The transition elements react with halogens at high temperatures to form transition metal
halides. These reactions have very high heat of reaction. But once the reaction starts, the heat of reaction is
sufficient to continue the reaction. The halogens react in the following decreasing order ; F
2
> Cl
2
> Br
2
> I
2
Table-8 : Halides of first transition series
Oxidation
Number
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+6 CrF
6
+5 VF
5
CrF
5
+4 TiX
4 VX
4
a
CrF
4
MnF
4
+3 ScX
3
TiX
3
VX
3
CrF
3
MnF
3 FeX
3
a
CoF
3
+2 TiX
2 VX
2
c
CrF
2
MnX
2
FeX
2
CoX
2
NiX
2 CuX
2
b
ZnX
2
+1
CuX
c
where X = F, Cl, Br, I, X
a
= F, Cl, Br, X
b
= F, Cl, X
c
= Cl, Br, I
Within each of the transition groups 3 - 12, there is a difference in the stability of the various oxidation states.
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. The following
trends are observed from table regarding transition metal halides :
(i) In general, the elements of first transition series tend to exist in lowoxidation states. Chromium to zinc form
stable difluorides and the other chlorides are also known.
(ii) Since fluorine is the most electronegative element, the transition metals showhighest oxidation states with
fluorine. The highest oxidation states are found in TiX
4
(tetrahalides, X = F, Cl, Br and I), VF
5
and CrF
6
.
(iii) The +7 oxidation state for Mn is not shown by simple halides. However, MnO
3
F is known in which the
oxidation state of Mn is +7.
(iv) After Mn, the tendency to show higher oxidation states with halogens are uncommon. Iron and cobalt form
trihalides FeX
3
(X = F, Cl or Br) and CoF
3
.
(v) The tendency of fluorine to stabilise the highest oxidation state is due to either higher lattice enthalpy as in
case of CoF
3
or higher bond enthalpy due to higher covalent bonds e.g., VF
5
and CrF
6
.
(vi) V(V) is shown by VF
5
only. However, the other halides undergo hydrolysis to form oxohalides, VOX
3
.
(vii) Fluorides are relatively unstable in their lowoxidation states. For example, vanadium form only VX
2
(X = Cl,
Br or I) and copper can form CuX (X = Cl, I). All copper (II) halides are known except the iodide. This is
because, Cu
2+
oxidises I

to I
2
.
2Cu
2+
+ 4I

Cu
2
I
2
(s) + I
2
It has been observed that many copper (I) compounds are unstable in aqueous solution and they undergo
disproportionation to Cu(II) and Cu(0) as :
2Cu
+
Cu
2+
+ Cu
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(A
hyd
H
O
) of Cu
2+
(aq) than Cu
+
, which is much more thancompensates
for the large energy required to remove the second electron i.e., second ionisation enthalpy of copper.
"manishkumarphysics.in"
10
CHEMISTRY
2. In metal oxides and oxocations.
Table-9 : Oxides of first transition series
Oxidation
Number
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+7 Mn
2
O
7
+6 CrO
3
+5 V
2
O
5
+4 TiO
2
V
2
O
4
CrO
2
MnO
2
+3 Sc
2
O
3
Ti
2
O
3
V
2
O
3
Cr
2
O
3
Mn
2
O
3
Fe
2
O
3
+2 TiO VO (CrO) MnO FeO CoO NiO CuO ZnO
+1 Cu
2
O
Mixed oxides Mn
3
O
4
Fe
3
O
4
Co
3
O
4
The ability of oxygen to stabilize the highest oxidation state is demonstrated in their oxides. The highest
oxidation states in their oxides concides with the group number. For example, the highest oxidation state of
scandium of group 3 is +3 in its oxides, Sc
2
O
3
whereas the highest oxidation state of manganese of group 7
is +7, in Mn
2
O
7
. However beyond group 7, no higher oxides of iron above Fe
2
O
3
are known. Although higher
oxidation state such as +6 is shown in ferrates such as FeO
4
2
inalkalinemedium, but they readily decompose
to Fe
2
O
3
and O
2
. Besides the oxides, oxocation of the metals also stabilise higher oxidation states. For
example, V
V
as VO
2
+
, V
IV
as VO
2+
and Ti
IV
as TiO
2+
. It may be noted that the ability of oxygen to stabilise
these high oxidation states exceeds that of fluorine. For example, manganese forms highest fluoride as
MnF
4
whereas the highest oxide is Mn
2
O
7
. This is due to the fact that oxygen has great ability to form
multiple bonds to metals. In the covalent oxide. Mn
2
O
7
, each Mn is tetrahedrally surrounded by oxygen
atoms and has MnOMn bridge. The tetrahedral [MO
4
]
n
ions are also known for vanadium (V), chromium
(VI), manganese (VI) and manganese (VII).
The transition elements in the +2 and +3 oxidation states mostly form ionic bonds whereas with higher
oxidation states, the bonds are essentially covalent e.g., in MnO
4

all bonds are covalent. As the oxidation


number of a metal increases, the ionic character of their oxides decrease. For example, in case of Mn,
Mn
2
O
7
is a covalent green oil. In these higher oxides the acidic character is predominant. Thus CrO
3
gives
H
2
CrO
4
and H
2
Cr
2
O
7
and Mn
2
O
7
gives HMnO
4
. V
2
O
5
is, however amphoteric though mainly acidic and with
alkalies as well as acids gives VO
4
3
and VO
2
+
respectively.
Example-7 For the first series of transition metals the E
O
values are
E
O
V Cr Mn Fe Co Ni Cu
(M
2+
/M
+1
) 1.18 0.91 1.18 0.44 0.28 0.25 + 0.34
Explain the irregularity in the above values.
Solution This is because of irregular variation of ionization energies (IE
1
+ IE
2
) and also the sublimation
energies which are much less for manganese and vanadium
Example-8 Write the formulae of different oxides of manganese. What is the oxidation state of manganese in
each of them ?Arrange them in order of their decreasing acidic character.
Solution Mn
+2
O, Mn
2
3+
O
3
, Mn
4+
O
2
, Mn
2
7+
O
7
, Mn
3
O
4
(mixed oxide of MnOand Mn
2
O
3
)
As the oxidation state of Mn increases, the electronegativity values of the central metal ions increase.
As a result of this the difference in the electronegativity values between metals and oxygen decrease.
So the acidic character increases as given below.
MnO < Mn
2
O
3
< MnO
2
< Mn
2
O
7
Example9 Name the oxometal anions of the first series of the transition metals in which the metal exhibits the
oxidation state equal to its group number.
Solution In Cr
2
O
7
2
and CrO
4
2
the oxidation state of Cr is +6 (2x + 7(2) = 2 and x + 4 ( 2) = 2) . The group
number is equal to the number of electrons in (n-1) d and ns sub-shells for d-block elements. So
group no. = 5 + 1 = 6.
In MnO
4

the oxidation state of Mn is +7 (2x + 7(2) = 1). The group number is equal to the number
of electrons in (n-1) d and ns sub-shells for d-block elements. So group no. = 5 + 2 = 7
"manishkumarphysics.in"
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CHEMISTRY
Example-10 Zinc does not showvariable valency because of :
(A) complete d sub-shell (B) inert pair effect (C) 4s
2
sub-shell (D) none.
Solution
30
Zn = [Ar]
18
3d
10
4s
2
. Zinc has completely filled d-sub-shell so removal of electron from completely
filled 4d sub-shell would be quite difficult. Thus it does not showvariable valency.
Therefore, (A) option is correct.
Formation of Coloured Ions :
Most of the compounds of transition metals are coloured in the solid formor solution form. The colour of the
compounds of transition metals may be attributed to the presence of incomplete (n 1) d-sub-shell. 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 intodifferent energy levels. This phenomenon is called crystal field splitting. For example,
when the six ions or molecules approach the metal ion (called octahedral field), the five d-orbitals split up into
two sets : one set consisting of two d-orbitals (
2 2 2
z y x
d , d

) of higher energies and the other set consisting of
three d-orbitals (d
xy
, d
yz
, d
zx
) of lower energies.
In the case of the transition metal ions, the electron can be easily promoted fromone energy level to another
in the same d-sub-shell. These are called d-d transitions. The amount of energy required to excite some of
the electrons to higher energy states within the same d-sub-shell corresponds to energy of certain colours of
visiblelight. Therefore, whenwhitelight falls on atransitionmetal compound, someof its energy corresponding
to a certain colour, is absorbed and the electron gets raised fromlower energy set of orbitals to higher energy
set of orbitals as shown below :
Figure showing electronic transition from t
2g
to e
g
orbitals.
The excess of other colours constituting white light are transmitted and the compound appears coloured. The
observedcolour of asubstanceis always complementarycolour of thecolour whichis absorbedbythesubstance.
For example, Ti
3+
compounds containoneelectronin d-sub-shell (d
1
). It absorbs greenandyellowportions from
the white light and blue and red portions are emitted. Therefore, Ti
3+
ions appear purple. Similarly, hydrated
cupric compounds absorb radiations corresponding to red light and the transmitted colour is greenish blue
(which is complementary colour to red colour). Thus, cupric compounds have greenish-blue colour.
Table-10 : Colour of different hydrated transition metal ions.
Ion Outer Configuration Colour of the ion
Sc (III), Ti (IV)
3d
0
Colourless
Ti (III)
3d
1
Purple
V (IV)
3d
1
Blue
V (III)
3d
2
Green
Cr (III)
3d
3
Green
Mn (III)
3d
4
Violet
Cr (II)
3d
4
Blue
Mn (II)
3d
5
Pink
Fe (III)
3d
5
Yellow
Fe (II)
3d
6
Green
Co (III)
3d
6
Blue
Co (II)
3d
7
Pink
Ni (II)
3d
8
Green
Cu (II)
3d
9
Blue
Cu (I)
3d
10
Colourless
Zn (II)
3d
10
Colourless
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CHEMISTRY
Example-11 Explain the blue colour of CuSO
4
.5H
2
O.
Solution Cu
2+
ion (3d
9
) absorbs red light from the visible region, for the promotion of 3d electrons, the ions
reflect blue light and appear blue.
Magnetic Properties
It is interesting to note that when the various substances are placed in a magnetic field, they do not behave
in a similar way i.e., they showdifferent behaviour which are known as magnetic behaviour.
These are classified as :
(i) 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.
(ii) Diamagnetic substances. The substances which are repelled by magnetic field are called diamagnetic
substances and this character arises due to the presence of paired electrons in the atomic orbitals.
Most of thecompounds of transitionelements areparamagnetic innatureandareattractedbythemagnetic field.
The transition elements involve the partial filling of d-sub-shells. Most of the transition metal ions or their
compounds have unpaired electrons in d-sub-shell (fromconfiguration d
1
to d
9
) and therefore, they give rise to
paramagnetic character. The magnetic character is expressed in terms of magnetic moment. The larger the
number of unpaired electrons in a substance, the greater is the paramagnetic character and larger is the
magnetic moment. The magnetic moment is expressed in Bohr magnetons abbreviated as B.M.
Table-11 : Calculated and observed magnetic moment of ions of first transition series.
Calculated observed
Sc
3+
3d
0
0 0 0
Ti
3+
3d
1
1 1.73 1.75
Ti
2+
3d
2
2 2.84 2.76
V
2+
3d
3
3 3.87 3.86
Cr
2+
3d
4
4 4.90 4.80
Mn
2+
3d
5
5 5.92 5.96
Fe
2+
3d
6
4 4.90 5.3 - 5.5
Co
2+
3d
7
3 3.87 4.4 - 5.2
Ni
2+
3d
8
2 2.84 2.9 - 3.4
Cu
2+
3d
9
1 1.73 1.8 - 2.2
Zn
2+
3d
10
0 0 0
Magnetic moment
(B.M.)
Number of unpaired electrons Outer Configuration Ion
The experimental data are mainly for hydrated ions in solution or in the solid state.
Each unpaired electron have magnetic moment associated with its spin angular momentum and orbital
angular momentum. In the compounds of first transition series, the orbital angular momentum does not
contribute much and thus has no significance. Therefore, for the first transition series elements, the magnetic
moment arise only from the spin of the electrons. This can be calculated from the relation :
= ) 2 n ( n + B.M.
where n is the number of unpaired electrons and is magnetic moment in Bohr magneton (BM) units.
Theparamagnetismfirst increases inanytransition series andthendecreases. Themaximumparamagnetism
is observed around the middle of the series (as contains maximumnumber of unpaired electrons).
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.
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CHEMISTRY
Example-12 Determine the magnetic moment of a divalent ion in aqueous solution if its atomic number is 25.
Solution The metal having atomic number 25 has electron configuration [Ar]
18
3d
5
4s
2
. So its divalent ion in
aqueous solution will have electron configuration [Ar]
18
3d
5
4s
0
. Thus it has five unpaired electrons.
So
(spin)
= ) 2 5 ( 5 + = 5.92 BM.
Formation of complexes :
Incontrast torepresentativeelements, the transitionelements formalarge number of coordinationcomplexes.
The transition metal ions bind to a number of anions or neutral molecules in these complexes. The common
examples are [Ni(NH
3
)
6
]
2+
, [Co(NH
3
)
6
]
3+
, [Fe(CN)
6
]
3
, [Fe(CN)
6
]
4
, [Cu(NH
3
)
4
]
2+
, etc.
The great tendency of transition metal ions to form complexes is due to :
(i) small size of the atoms and ions, (ii) high nuclear charge and (iii) 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
They are generally non-stoichiometric and are neither typically ionic nor covalent. The common examples of
interstitial compounds of transition metals are TiC, Mn
4
N, Fe
3
H, TiH
2
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 TiH
1.7
, VH
0.56
, etc. Because of the nature of their composition, these
compounds are referred to as interstitial compounds.
As a result of the filling up of the interstitial spaces, the transition metals become rigid and hard. These
interstitial compounds have similar chemical properties as the parent metals but differ significantly in their
physical properties particularly, density, hardness and conductivity. For example, steel and cast iron are
hard because they form interstitial compounds with carbon.
The transition metals can easily accommodate the small non-metallic atoms because of void sites between
the packed atoms of the crystalline metal. These spaces are present because of defects in their structures
and existence of variable oxidation states.
The general characteristic physical and chemical properties of these compounds are :
(i) They have high melting points which are higher than those of pure metals.
(ii) They retain metallic conductivity i.e. of pure metals.
(iii) They are very hard and some borides have hardness as that of diamond.
(iv) They are chemically inert.
Catalytic properties
Many transition metals and their compounds act as good catalysts for various reactions. Of these, the use
of Fe, Co, Ni, V, Cr, Mn, Pt, etc. are very common.
For example,
"manishkumarphysics.in"
14
CHEMISTRY
(i) Iron-molybdenum is used as catalyst in the synthesis of ammonia by Habers process.
(ii) Nickel is used in hydrogenation reactions in organic chemistry.
(iii) V
2
O
5
is used for the oxidation of SO
2
to SO
3
in the Contact process for the manufacture of H
2
SO
4
.
(iv) MnO
2
is used to catalyse the decomposition of H
2
O
2
solution.
(v) Cobalt salts catalyse the decomposition of bleaching powder.
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.
Thesereactionintermediates readilydecomposeyieldingtheproducts andregeneratingtheoriginal substance.
The transition metals form these reaction intermediates due to the presence of vacant orbitals or their
tendency to form variable oxidation states.
(i) In some cases, the transition metal catalysts provide a suitable large surface area for the adsorption of the
reactant. This increases the concentration of the reactants at the catalyst surface and also weakens the
bonds in the reactant molecules. Consequently, the activation energy gets lowered.
For example, during the conversion of SO
2
to SO
3
, V
2
O
5
is used as a catalyst. Solid V
2
O
5
adsorbs a molecule
of SO
2
on the surface to form V
2
O
4
and the oxygen is given to SO
2
to form SO
3
. The divanadium tetroxide is
then converted to V
2
O
5
by reaction with oxygen :
V
2
O
5
+ SO
2
(catalyst) SO
3
+ V
2
O
4
(divanadium tetroxide)
2V
2
O
4
+ O
2
2V
2
O
5
(ii) In some cases, the transition metal ions can change their oxidation states and become more effective as
catalysts. For example, cobalt salts catalyse decomposition of bleaching powder as cobalt can easily
change oxidation state from +2 to +3 as :
Co
2+
+ OCl

+ H
2
O Co
3+
+ Cl

+ 2OH

2Co
3+
+ 2OH

2Co
2+
+ H
2
O + O
2
Iron (III) also catalyses the reaction between iodide and persulphate ions (S
2
O
8
2
).
Example-13 Howiron (III) catalyses the reaction between iodide &persulphate?
Solution 2Fe
3+
+ 2I

2Fe
2+
+ I
2
2Fe
2+
+ S
2
O
8
2
2Fe
3+
+ 2SO
4
2
________________________________________________________
2I

+ S
2
O
8
2

III ) ( Fe
I
2
+ 2 SO
4
2
Alloy Formation :
Alloys are homogeneous solid solutions in which the atoms of one metal are distributed randomly among the
atoms of the other metal. The alloys are generally formed by those atoms which have metallic radii within
about 15% of each other. Transition metals form a large number of alloys. The transition metals are quite
similar in size and, therefore, the atoms of one metal can substitute the atoms of other metal in its crystal
lattice. Thus, on cooling a mixture solution of two or more transition metals, solid alloys are formed. Such
alloys are hard, have high melting points and are more resistant to corrosion than parent metals.
For example, the most common known alloys are ferrous alloys. Chromium, manganese, vanadium, tungsten,
molybdenum etc. are used to produce variety of steels and stainless steel. Alloys of transition metals with
non-transition metals such as bronze (copper-tin), brass (copper-zinc) are also industrially important alloys.
Figure showing formation of alloys
"manishkumarphysics.in"
15
CHEMISTRY
Example-14 Which of the following form an alloy ?
(A) Ag + Pb (B) Fe + Hg (C) Pt + Hg (D) Fe + C
Solution Argentiferrous lead is an alloy contains Ag & Pb.
'Fe' and 'C' form an alloy called cementite, Fe
3
C.
Therefore, (A) &(D) option are correct.
PREPARATIONS AND PROPERTIES OF SOME IMPORTANT d-BLOCK METAL COMPOUNDS
[A] COMPOUNDSOF IRON:
Ferrous Sulphate, FeSO
4
.7H
2
O (Green vitriol)
It is commonly known as harakasis
Preparation
(i) By iron scrap :
Fe + H
2
SO
4
FeSO
4
+ H
2
|
(ii) From kipp's waste :
3FeS
2
+ 2H
2
O + 11O
2
FeSO
4
+ Fe
2
(SO
4
)
3
+ 2H
2
SO
4
Fe
2
(SO
4
)
3
+ Fe 3FeSO
4
(iii) FeCO
3
+ H
2
SO
4
FeSO
4
+ H
2
O + CO
2
Properties
(a) Physical : Hydrated ferrous sulphate is a green crystalline compound, effloresces on exposure to air.
Anhydrous FeSO
4
is colourless.
(b) Chemical :
(i) On exposure to atmosphere, it turns brownish-yellowdue to the formation of basic ferric sulphate.
4FeSO
4
+ 2H
2
O + O
2
4Fe(OH) . SO
4
(basic ferric sulphate)
(ii) Aqueous solution is acidic due to hydrolysis.
Fe
2+
+ 2H
2
O Fe(OH)
2
+ 2H
+
(iii) FeSO
4
. 7H
2
O
C 140
FeSO
4
. H
2
O
C 300
2FeSO
4
. Temp
High

Fe
2
O
3
+ SO
2
| + SO
3
|
(iv) FeSO
4
+ 6KCN K
4
[Fe(CN)
6
] + K
2
SO
4
(v) It acts as reducing agent.
AuCl
3
+ 3FeSO
4
Au + Fe
2
(SO
4
)
3
+ FeCl
3
6HgCl
2
+ 6FeSO
4
3Hg
2
Cl
2
+ 2Fe
2
(SO
4
)
3
+ 2FeCl
3
MnO
4

+ 8H
+
+ 5Fe
2+
5Fe
3+
+ Mn
2+
+ 4H
2
O
Cr
2
O
7
2
+ 14H
+
+ 6Fe
2+
6Fe
3+
+ 2Cr
3+
+ 7H
2
O
Uses : It is used :
(i) for making Blue - Black ink.
(ii) as mordant in dyeing
(iii) as insecticide in agriculture
(iv) for making laboratory reagents like Mohr's salt etc.
FeSO
4
+ (NH
4
)
2
SO
4
+ 6H
2
O) FeSO
4
(NH
4
)
2
SO
4
.6H
2
O(Mohr's salt)
(v) FeSO
4
+ H
2
O
2
known as Fenton's reagent is used as catalyst.
Ferric Oxide, Fe
2
O
3
:
Preparation :
(i) 2Fe(OH)
3

A
Fe
2
O
3
+ 3H
2
O
(ii) 2FeSO
4

A
Fe
2
O
3
+ SO
2
+ SO
3
(iii) 4FeS + 7O
2
2Fe
2
O
3
+ 4SO
2
"manishkumarphysics.in"
16
CHEMISTRY
Properties :
(a) Physical : It is a deep red powder and is insoluble in water.
(b) Chemical :
(i) Amphoteric nature of iron (III) oxide.
Fe
2
O
3
+ 6HCl 2FeCl
3
+ 3H
2
O
Fe
2
O
3
+ 2NaOH

fusion
H
2
O+ 2NaFeO
2
Fe
2
O
3
+ Na
2
CO
3

fusion
2NaFeO
2
+ CO
2
NaOCl and chlorine oxidises the NaFeO
2
in to Na
2
FeO
4
.
NaFeO
2
+ Cl
2
+ 4NaOH 2Na
2
FeO
4
+ 2NaCl + 2H
2
(ii) 6Fe
2
O
3

C 1300
4Fe
3
O
4
+ O
2
(iii) Fe
2
O
3
+ 3H
2
2Fe + 3H
2
O
Uses : It is used as (i) a red pigment, (ii) an abrasive polishing powder and (iii) a catalyst.
Ferric Chloride, FeCl
3
:
Preparation :
(a) Anhydrous FeCl
3
:
(i) 12FeCl
2
(anhydrous) + 3O
2

A
2Fe
2
O
3
+ 8FeCl
3
(ii) 2Fe + 3Cl
2
(dry)

A
2FeCl
3
(iii) FeCl
3
. 6H
2
O + 6SOCl
2
FeCl
3
+ 12HCl + 6SO
2
(iv) FeCl
3
.6H
2
O+ 6CH
3

3
3
3
OCH
|
CH C
|
OCH

FeCl
3
+ 12CH
3
OH+ 6CH
3
COCH
3
(b) Hydrated FeCl
3
:
(i) Fe(OH)
3
+ 3HCl

FeCl
3
+ 3H
2
O
(ii) Fe
2
O
3
+ 6HCl

2FeCl
3
+ 3H
2
O
(iii) Fe
2
(CO
3
)
3
+ 6HCl

2FeCl
3
+ 3H
2
O+ 3CO
2
(iv) 2Fe + 4HCl + Cl
2

2FeCl
3
+ 2H
2
|
All solutions of FeCl
3
obtained in above chemical reactions on crystallisation gives hydrated
FeCl
3
.6H
2
O.
Properties
(a) Physical :
Anhydrous ferric chloride is dark black solid while hydrated salt, FeCl
3
. 6H
2
Ois yellowish-brown deliquescent
crystalline solid. Both are soluble in water as well as in ether forming solvated species,
[Fe(H
2
O)
4
Cl
2
]Cl . 2H
2
Oand O

FeCl
3
respectively..
It is sublimed at 300C giving a dimeric gas, .
(b) Chemical :
(i) Action of heat :
(a) 2FeCl
3
(anhydrous)

A
2FeCl
2
+ Cl
2
(b) 2[FeCl
3
. 6H
2
O]

A
Fe
2
O
3
+ 6HCl + 9H
2
O
(ii) Aqueous solution is acidic due to hydrolysis.
[Fe(H
2
O)
6
]
3+
+ H
2
O [Fe(H
2
O)
5
(OH)]
2+
+ H
3
O
+
acid base base acid
(iii) As oxidising agent : 2FeCl
3
+ SnCl
2
2FeCl
2
+ SnCl
4
2FeCl
3
+ H
2
S 2FeCl
2
+ 2HCl + S
2FeCl
3
+ SO
2
+ 2H
2
O 2FeCl
2
+ H
2
SO
4
+ 2HCl
2FeCl
3
+ 2KI 2FeCl
2
+ 2KCl + I
2
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CHEMISTRY
(iv) Formation of addition compounds :
FeCl
3
+ 6NH
3
FeCl
3
. 6NH
3
; FeCl
3
+ NOCl FeCl
3
.NOCl
(v) 2FeCl
3
+ 3Na
2
CO
3
+ 3H
2
O 2Fe(OH)
3
+ 6NaCl + 3CO
2
Uses :
It is used :
(i) as a medicine (its alcoholic solution named as tincture is ferri perchloride).
(ii) for detection of acetates and phenols.
(iii) for making prussian blue dye.
(iv) as an oxidising agent.
[B] COMPOUNDSOF ZINC:
Zinc oxide, ZnO (Chinese white or philosopher's wool)
It is found in nature as zincite or red zinc ore.
Preparation :
(i) 2Zn + O
2
2ZnO (ii) ZnCO
3

A
ZnO+ CO
2
(iii) 2Zn(NO
3
)
2

A
2ZnO+ 4NO
2
+ O
2
(iv) Zn(OH)
2

A
ZnO+ H
2
O
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 400C.
(b) Chemical :
(i) It is amphoteric in nature.
ZnO + H
2
SO
4
ZnSO
4
+ H
2
O
ZnO+ 2NaOH Na
2
ZnO
2
+ H
2
O
(ii) ZnO + H
2
C 400

A
Zn + H
2
O
Uses :
It is used :
(i) as a white paint. It does not get tarnished even in presence of H
2
S because ZnS is also white.
(ii) for preparing Rinmann's green (Green paint - ZnCoO
2
)
(iii) as catalyst for preparation of methyl alcohol
(iv) for making soft rubber
(v) for making cosmetic powders, creams and in medicine
Example-15 Zn(OH)
2

A
[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 Xin dilute HCl gives bluish white/whiteprecipitatewithexcess potassiumferrocyanide.
(D) X is insoluble in aqueous sodium hydroxide.
Solution (A) X is ZnOwhich on heating with cobalt nitrate gives ZnO. CoO, the Rinmann's green.
(B) It turns yellow on heating and becomes white on cooling.
(C) ZnCl
2
forms bluish white/white precipitate. Zn
3
K
2
[Fe(CN)
6
]
2
.
3 Zn
2+
+ 2 K
+
+ 2 [Fe(CN)
6
]
4

K
2
Zn
3
[Fe(CN)
6
]
2
+
(D) ZnO+ 2NaOH Na
2
ZnO
2
(soluble complex) + H
2
O.
So options A, B & C are correct and (D) is incorrect.
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18
CHEMISTRY
Zinc Sulphate, ZnSO
4
. 7H
2
O (White vitriol)
Preparation :
(i) Zn + H
2
SO
4
ZnSO
4
+ H
2
(ii) ZnO + H
2
SO
4
ZnSO
4
+ H
2
O
(iii) ZnCO
3
+ H
2
SO
4
ZnSO
4
+ H
2
O+ CO
2
Properties :
(a) Physical : It is a colourless, crystalline solid soluble in water. It slowly effloresces when exposed to air.
It is isomorphous with Epsom salt (MgSO
4
. 7H
2
O)
(b) Chemical :
(i) ZnSO
4
+ 2NaOH Zn(OH)
2
+ (white) + Na
2
SO
4
Zn(OH)
2
+ 2NaOH Na
2
ZnO
2
(soluble complex) + 2H
2
O
(ii) ZnSO
4
+ 2NaHCO
3
ZnCO
3
+ Na
2
SO
4
+ H
2
O+ CO
2
(iii) ZnSO
4
.7H
2
O
C 100
ZnSO
4
. 6H
2
O
C 280
ZnSO
4

C 800
ZnO+ SO
3
Uses :
It is used :
(i) as eye lotion, (ii) for making lithophone - mixture of BaS + ZnSO
4
(white paint) and (iii) as mordant in
dyeing
Zinc Chloride ZnCl
2
.2H
2
O
Preparation :
It is prepared by dissolving zinc oxide, carbonate or hydroxide in dilute hydrochloric acid
ZnO+ 2HCl ZnCl
2
+ H
2
O
The solution so obtained on concentration and cooling gives the crystals of ZnCl
2
. 2H
2
O.
Anhydrous zinc chloride cannot be prepared merely by heating the crystals of ZnCl
2
. 2H
2
O because
a basic chloride Zn(OH)Cl is formed during decomposition which on further heating gives ZnO.
ZnCl
2
. 2H
2
O Zn(OH)Cl + HCl + H
2
O
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 + Cl
2

A
ZnCl
2
; Zn + HgCl
2
ZnCl
2
+ Hg
Properties :
It is a white crystalline solid, deliquescent and soluble in water. On heating it forms the oxychloride and
finally the oxide. Its concentrated solution sets to a hard mass when mixed with zinc oxide and
the product is used as a dental filling.
[C] COMPOUNDSOF COPPER
Copper Sulphate, CuSO
4
. 5H
2
O (Blue Vitriol)
It is also called 'Nilathotha'.
Preparation :
(i) CuO + H
2
SO
4
CuSO
4
+ H
2
O
(ii) Cu(OH)
2
+ H
2
SO
4
CuSO
4
+ 2H
2
O
(iii) Cu + H
2
SO
4
+
1
2
O
2
CuSO
4
+ H
2
O
(iv) CuCO
3
.Cu(OH)
2
(malachite ore) + 2H
2
SO
4
2CuSO
4
+ 3H
2
O+ CO
2
|
Properties
(a) Physical : It is a blue crystalline compound and is soluble in water.
(b) Chemical :
(i) CuSO
4
+ 2NaOH Cu(OH)
2
+
(blue) + Na
2
SO
4
2CuSO
4
+ Na
2
CO
3
+ H
2
O Cu(OH)
2
+
(blue) + Na
2
SO
4
+ CO
2
|
.
(ii) 2CuSO
4
+ SO
2
+ 2H
2
O + 2KI CuI
2
+ 2H
2
SO
4
+ K
2
SO
4
2CuSO
4
+ 2FeSO
4
+ 2KI Cu
2
I
2
+ Fe
2
(SO
4
)
3
+ K
2
SO
4
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CHEMISTRY
(iii) CuSO
4
+ Fe Cu + FeSO
4
CuSO
4
+ Zn Cu + ZnSO
4
(iv) 2CuSO
4
+ 2KSCN + SO
2
+ 2H
2
O 2CuSCN
+
(white) + K
2
SO
4
+ 2H
2
SO
4
(v) CuSO
4
.5H
2
O
s effloresce
air
CuSO
4
.4H
2
O
C 100
CuSO
4
. H
2
O
C 250
CuSO
4

C 750
CuO+SO
2
+O
2
Uses :
It is used :
(i) for making other copper compounds.
(ii) for electroplating, electrotyping, as mordant in dyeing.
(iii) in making Bordeaux mixture which is used in agriculture as fungicide and germicide.
(iv) in making Fehling's solution.
(v) in medicine as antiseptic.
(vi) in electric batteries.
Example-16 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.
Solution As 1%solution of (A) produced violet colouration with white portion of egg (Biuret test) and (A) with
potassiumiodidegives brownprecipitatewhichturnedwhiteonaddinghypo. The(A) maybeanhydrous
CuSO
4
(White). This is further confirmed by the reaction of (A) with potassium cyanide.
2CuSO
4
+ 4KI

Cu
2
I
2
+ (white) + I
2
| (yellow or brown) + 2K
2
SO
4
(A) (B)
I
2
+ 2Na
2
S
2
O
3

Na
2
S
4
O
6
+ 2NaI
2CuSO
4
+4KCN

2 Cu(CN)
2
+(yellow) +2K
2
SO
4
; 2Cu(CN)
2

2CuCN
+
(white) +(CN)
2
|
2 CuCN + 6 KCN

2 K
3
[Cu(CN)
4
] (colourless soluble complex).
(C)
Example-17 CuSO
4
.5H
2
O
C 100
[X] (s)
C 250
[Y] (s)
(A) X and Y are CuSO
4
. 3H
2
Oand CuSO
4
(B) X and Y are CuSO
4
. 3H
2
Oand CuSO
4
. H
2
O
(C) X and Y are CuSO
4
. H
2
Oand CuSO
4
(D) X and Y are CuSO
4
and CuO
Solution CuSO
4
.5H
2
O
C 100
CuSO
4
.H
2
O(s)
C 250
CuSO
4
(s).
So, (C) option is correct.
Cupric Oxide, CuO
It is called black oxide of copper and is found in nature as tenorite.
Preparation : It is prepared
(i) By heating Cu
2
O in air or by heating copper for a long time in air (the temperature should not
exceedabove 1100C)
2Cu
2
O+ O
2

4CuO
2Cu + O
2

2CuO
(ii) Cu(OH)
2

A
CuO+ H
2
O
(iii) 2Cu(NO
3
)
2

A
2CuO+ 4NO
2
+ O
2
(iv) On a commercial scale, it is obtained by heating/calcination of malachite which is found in nature.
CuCO
3
. Cu(OH)
2
2CuO+ CO
2
+ H
2
O
Properties
(a) Physical :
It is black powder insoluble in water and stable to moderate heating.
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CHEMISTRY
(b) Chemical :
(i) The oxide dissolves in acids HCl, H
2
SO
4
of HNO
3
forming corresponding salts.
CuO + 2H
+
Cu
2+
+ H
2
O
(ii) When heated to 1100 1200C, it is converted into cuprous oxide with evolution of oxygen.
4CuO 2Cu
2
O+ O
2
(iii) It is reduced to metallic copper by reducing agents like hydrogen, carbon and carbon monoxide.
CuO + H
2
Cu + H
2
O
Cupric Chloride, CuCl
2
. 2H
2
O
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 + O
2
2CuCl
2
+ 2H
2
O
CuO + 2HCl CuCl
2
+ H
2
O
Cu(OH)
2
CuCO
3
+ 4HCl 2CuCl
2
+ 3H
2
O+ CO
2
(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 150C.
Cu + Cl
2
CuCl
2
CuCl
2
. 2H
2
O
gas HCl
C 150
CuCl
2
+ 2H
2
O
Properties
(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 yellowwhen concentrated HCl is added. The blue colour is due to
complex cation [Cu(H
2
O)
4
]
2+
and yellow colour due to complex anion [CuCl
4
]
2
and green when both are
present.
(b) Chemical :
(i) The aqueous solution is acidic due to its hydrolysis
CuCl
2
+ 2H
2
O Cu(OH)
2
+ 2HCl
(ii) The anhydrous salt on heating forms Cu
2
Cl
2
and Cl
2
2CuCl
2
Cu
2
Cl
2
+ Cl
2
3CuCl
2
. 2H
2
O
Strong

A
CuO + Cu
2
Cl
2
+ 2HCl + Cl
2
+ 5H
2
O
(iii) It is readily reduced to Cu
2
Cl
2
by copper turnings or sulphur dioxide gas or nascent
hydrogen (obtained by the action of HCl on Zn) or SnCl
2
.
CuCl
2
+ Cu Cu
2
Cl
2
2CuCl
2
+ SO
2
+ 2H
2
O Cu
2
Cl
2
+ 2HCl + H
2
SO
4
2CuCl
2
+ 2H Cu
2
Cl
2
+ 2HCl
2CuCl
2
+ SnCl
2
Cu
2
Cl
2
+ SnCl
4
(iv) A pale blue precipitate of basic cupric chloride CuCl
2
. 3Cu(OH)
2
is obtained when NaOHis added.
CuCl
2
+ 2NaOH Cu(OH)
2
+ 2NaCl
CuCl
2
+ 3Cu(OH)
2
CuCl
2
. 3Cu(OH)
2
+
It dissolves in ammonium hydroxide forming a deep blue solution. On evaporation of this solution
deep blue crystals of tetraammine cupric chloride are obtained.
CuCl
2
+ 4NH
4
OH [Cu(NH
3
)
4
]Cl
2
. H
2
O+ 3H
2
O
[D] COMPOUNDSOF SILVER:
Silver Nitrate, AgNO
3
(Lunar caustic) :
Preparation :
It is prepared by heating silver with dilute nitric acid. The solution is concentrated and cooled when the
crystals of silver nitrate separate out.
3Ag + 4HNO
3
(dilute)
heat
3AgNO
3
+ NO + 2H
2
O
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CHEMISTRY
Properties
(a) Physical :
It is a colourless crystalline compound, soluble in water and alcohol. It melts at 212C.
(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.
2AgNO
3
2AgNO
2
+ O
2
When heated red hot, it gives metallic silver
2AgNO
3
2Ag + 2NO
2
+ O
2
(iii) Solutions of halides, phosphates, sulphides, chromates, thiocyanates, sulphates and thiosulphates,
all give a precipitate of the corresponding silver salt with silver nitrate solution (for reactions refer
qualitative analysis sheet).
(iv) SolidAgNO
3
absorbs ammonia gas with the formation of an addition compound, AgNO
3
. 3NH
3
.
When NH
4
OH is added to silver nitrate solution, a brown precipitate of silver oxide appears which
dissolves in excess of ammonia forming a complex salt.
2AgNO
3
+ 2NH
4
OH Ag
2
O+ 2NH
4
NO
3
+ H
2
O
Ag
2
O+ 2NH
4
NO
3
+ 2NH
4
OH 2[Ag(NH
3
)
2
]NO
3
+ 3H
2
O
(v) The ammonical solution of AgNO
3
react with acetylene to form a white precipitate.
2AgNO
3
+ 2NH
4
OH+ C
2
H
2
Ag
2
C
2
+ (silver acetylide) + 2NH
4
NO
3
+ 2H
2
O
(vi) Ammonical silver nitrate is called Tollens reagent and is used to identify reducing sugars and
aldehydes.
RCHO + 2Ag
+
+ 3OH


A
RCOO

+ 2Ag+ + 2H
2
O
It is known as silver mirror test of aldehydes and reducing sugars.
Ag
2
O + HCHO 2Ag + HCOOH
Ag
2
O+ C
6
H
12
O
6
2Ag + C
6
H
12
O
7
(vii) Reaction with iodine :
(a) 6AgNO
3
(excess) + 3I
2
+ 3H
2
O AgIO
3
+ 5AgI + 6HNO
3
(b) 5AgNO
3
+ 3I
2
(excess) + 3H
2
O HIO
3
+ 5AgI+ 5HNO
3
(viii) Silver is readily displaced from an aqueous silver nitrate solution by the base metals, particularly, if
the solution is some what acidic.
2AgNO
3
+ Cu 2Ag + Cu(NO
3
)
2
2AgNO
3
+ Zn 2Ag + Zn(NO
3
)
2
(ix) Phosphine, arsine and stibine all precipitate silver from silver nitrate solution
PH
3
+ 6AgNO
3
+ 3H
2
O 6Ag + 6HNO
3
+ H
3
PO
3
AsH
3
+ 6AgNO
3
+ 3H
2
O 6Ag + 6HNO
3
+ H
3
AsO
3
Uses :
(i) It is used as a laboratory reagent for the identification of various acidic radicals especially for chloride,
bromide and iodide. The ammonical silver nitrate solution i.e., Tollen's reagent is used in organic
chemistry for testing aldehydes, reducing sugars, etc.
(ii) Silver nitrate is used for making silver bromide which is used in photography.
(iii) It is used in the preparation of making inks and hair dyes.
(iv) It is used extensively for the preparation of silver mirrors. The process of depositing a thin and
uniform layer of silver on a clean glass surface is known as silvering of mirrors. It is employed for
making looking glasses, concave mirrors and reflecting surfaces. The process is based on the
reduction of ammonical silver nitrate solution by some reducing agent like HCHO. The silver film
deposited on the glass is first coated with a varnish and finally painted with red lead to prevent its
being scraped off.
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CHEMISTRY
Silver oxide (Ag
2
O) :
Preparation :
It is prepared as brown solid by adding sodium hydroxide solution to silver nitrate solution.
2AgNO
3
+ 2NaOH Ag
2
O+ 2NaNO
3
+ H
2
O
Properties :
It is a brown solid sparingly soluble in water.
(i) On heating, it is decomposed to black metallic silver with evolution of oxygen at 160C.
2Ag
2
O
A
4Ag + O
2
|
(ii) It is reduced to the metal by hydrogen on heating
Ag
2
O + H
2

A
2Ag + H
2
O
(iii) The aqueous solution is strongly basic, solution behaving as AgOH. Moist silver oxide hydrolyses
the alkyl halide to alcohol.
C
2
H
5
Br +AgOH C
2
H
5
OH +AgBr
(iv) Dry distillation of a mixture of alkyl halide with silver oxide produces ether.
2C
2
H
5
Br +Ag
2
O
A
C
2
H
5
O C
2
H
5
+ 2AgBr
Uses :
It is used :
As Tollens reagent for the detection of aldehydes, formic acid and terminal alkynes.
In the manufacture of mirrors.
Photography :
A photographic film consists of a light sensitive emulsion of fine particles (grains) of silver salts in gelatine
spread on a clear celluloid strip or a glass plate. The grain size is very important to photographers, as this
affects the quality of the pictures produced. AgBr is mainly used as the light sensitive material. SomeAgI is
used in fast emulsions.
The film is placed in a camera. When the photograph is exposed, light from the subject enters the camera
and is focussed by the lens to give a sharp image on the film. The light starts a photochemical reaction by
exciting a halide ion, which loses an electron. The electron moves in a conduction band to the surface of the
grain, where it reduces a Ag
+
ion to metallic silver.
2AgBr(s)
light
2Ag + Br
2
In modern photography only a short exposure of perhaps 1/100th of a second is used. In this short time, only
a few atoms of silver (perhaps 1050) are produced in each grain exposed to light. Parts of the film which
have been exposed to the bright parts of the subject contain a lot of grains with some silver. Parts exposed
to paler parts of the subject contains a few grains with some silver, whilst parts not exposed contain none.
Thus the film contains a latent image of the subject. However, the number of silver atoms produced is so
small that the image is not visible to the eye.
Next the film is placed a developer solution. This is a mild reducing agent, usually containing quinol. Its
purpose is to reduce more silver halide toAg metal. Ag is deposited mainly where there are already someAg
atoms. Thus the developing process intensifies the latent image on the film so it becomes visible. The
correct conditions for processing must be used to obtain an image of the required blackness.
2AgBr(s) + 2OH

(aq) + HO OH(aq) 2Ag(s) + 2H


2
O() + O O+ 2Br

(aq)
hydroquinol hydroquinone
If the film was brought out into daylight at this stage, the unexposed parts of the emulsion would turn black
and thus destroy the picture. To prevent this happening any unchanged silver halides are removed by placing
the film in a fixer solution. Asolution of sodium thiosulphate is used as fixer. It forms a soluble complex with
silver halides.
AgBr + 2Na
2
S
2
O
3
Na
3
[Ag(S
2
O
3
)
2
] + NaBr
After fixing, the filmcan safely be brought out into daylight. Parts blackened by silver represent the light parts
of the original picture. This is therefore a negative.
To obtain an image with light and dark the right way round, a print must be made. Light is passed through the
negative onto a piece of paper coated withAgBr emulsion. This is then developed and fixed in the same way
as before.
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CHEMISTRY
[E] POTASSIUMPERMANGANATE (KMnO
4
) :
Preparation
This is the most important and well known salt of permanganic acid and is prepared from the pyrolusite ore.
It is prepared by fusing pyrolusite ore either with KOH or K
2
CO
3
in presence of atmospheric oxygen or any
other oxidising agent such as KNO
3
. Thefused mass turns green with the formation of potassiummanganate,
K
2
MnO
4
.
2MnO
2
+ 4KOH + O
2
2K
2
MnO
4
+ 2H
2
O
2MnO
2
+ 2K
2
CO
3
+ O
2
2K
2
MnO
4
+ 2CO
2
The fused mass is extracted with water and the solution is nowtreated with a current of chlorine or ozone or
carbon dioxide to convert manganate into permanganate.
2K
2
MnO
4
+ Cl
2
2KMnO
4
+ 2KCl
2K
2
MnO
4
+ H
2
O + O
3
2KMnO
4
+ 2KOH + O
2
3K
2
MnO
4
+ 2CO
2
2KMnO
4
+ MnO
2
+ 2K
2
CO
3
Commercially it is prepared by fusion of MnO
2
with KOH followed by electrolytic oxidation of manganate.
MnO
4
2
(green) MnO
4

(purple) + e

In the laboratory, a manganese(II) ion salt is oxidised by peroxodisulphate to permanganate


2Mn
2+
+ 5S
2
O
8
2
+ 8H
2
O 2MnO
4

+ 10SO
4
2
+ 16H
+
Properties
(a) Physical :
It is purple coloured crystalline compound. It is moderately soluble in water at room temperature.
(b) Chemical :
(i) Effect of heating
When heated alone or with an alkali, it decomposes evolving oxygen.
2KMnO
4

K 750
K
2
MnO
4
+ MnO
2
+ O
2
2K
2
MnO
4
Heat
d Re

2K
2
MnO
3
+ O
2
4KMnO
4
+ 4KOH
A
4K
2
MnO
4
+ 2H
2
O + O
2
or
4MnO
4

+ 4OH


A
4MnO
4
2
+ O
2
+ 2H
2
O.
MnO
4
2
in dilute alkaline, water and acidic solutions is unstable and disproportionates to give MnO
4

and
MnO
2
.
3MnO
4
2
+ 4H
+
2MnO
4

+ MnO
2
+
+ 2H
2
O
3MnO
4
2
+ 2H
2
O 2MnO
4

+ MnO
2
+
+ 4OH

or
3MnO
4
2
+ 3H
2
O 2MnO
4

+ MnO(OH)
2
+
+ 4OH

On heating in current of H
2
, solid KMnO
4
gives MnO
2KMnO
4
+ 5H
2

A
2KOH + 2MnO + 4H
2
O
(ii) On treatment with concentrated H
2
SO
4
(KMnO
4
is taken in excess), it forms manganese heptoxide
via permanganyl sulphate which decomposes explosively on heating.
2KMnO
4
+ 3H
2
SO
4
2KHSO
4
+ (MnO
3
)
2
SO
4
+ 2H
2
O
(MnO
3
)
2
SO
4
+ H
2
O Mn
2
O
7
+ H
2
SO
4
Mn
2
O
7
2MnO
2
+
3
2
O
2
KMnO
4
+ 3H
2
SO
4
(conc.) K
+
+ MnO
3
+
(green) + 3HSO
4

+ H
3
O
+
.
"manishkumarphysics.in"
24
CHEMISTRY
(iii) Potassium permanganate is a powerful oxidising agent.
Potassium permanganate acts as an oxidising agent in alkaline, neutral or acidic solutions.
Amixture of sulphur, charcoal and KMnO
4
forms an explosive powder. Amixture of oxalic acid and
KMnO
4
catches fire spontaneous after a few seconds. The same thing happens when glycerine is
poured over powdered KMnO
4
.
In alkaline & neutral medium :
In strongly alkaline medium KMnO
4
is reduced to manganate.
2KMnO
4
+ 2KOH (conc.)

2K
2
MnO
4
+ H
2
O + [O]
or
e

+ MnO
4


MnO
4
2
However if solution is dilute then K
2
MnO
4
is converted in to MnO
2
which appears as a brownish
precipitate.
2K
2
MnO
4
+ 2H
2
O

2MnO
2
+ 4KOH + 2[O]
or
2e

+ 2H
2
O + MnO
4
2

MnO
2
+ 4OH

This type of behaviour is shown by KMnO


4
itself in neutral medium
3e

+ 2H
2
O + MnO
4


MnO
2
+ 4OH

In alkaline or neutral medium KMnO


4
shows following oxidising properties.
(a) It oxidises ethene to glycol.
In alkaline medium KMnO
4
solution is also known as Bayers reagent (1%alkaline KMnO
4
solution).
(b) It oxidises iodide into iodate.
3e

+ 2H
2
O + MnO
4


MnO
2
+ 4OH

[2]
6OH

+ I


IO
3

+ 3H
2
O + 6e

2MnO
4

+ I

+ H
2
O

2MnO
2
+ IO
3

+ 2OH

(c) H
2
S is oxidised into sulphur :
2MnO
4

+ 3H
2
S

2MnO
2
+ 2OH

+2H
2
O + 3S
(d) Manganese sulphate is oxidised to MnO
2
:
2MnO
4

+ 3MnSO
4
+ 2H
2
O K
2
SO
4
+ 5MnO
2
+ 2H
2
SO
4
(e) In neutral/ faintly alkaline solution thiosulphate is quantitatively oxidised to sulphate.
8MnO
4

+ 3S
2
O
3
2
+ H
2
O 8MnO
2
+ 6SO
4
2
+ 2OH

(f) In the presence of sodium hydroxide, sodium sulphite is oxidised in to sodium sulphate.
2MnO
4

+ 3SO
3
2
+ 3H
2
O 2MnO(OH)
2
+
+ 3SO
4
2
+ 2OH

.
In acidic medium (in presence of dilute H
2
SO
4
) :
Manganous sulphate is formed. The solution becomes colourless.
2KMnO
4
+ 3H
2
SO
4
K
2
SO
4
+ 2MnSO
4
+ 3H
2
O + 5[O]
or MnO
4
+ 8H
+
+ 5e

Mn
2+
+ 4H
2
O
This medium is used in quantitative (volumetric) estimations. The equivalent mass of KMnO
4
in
acidic medium is =
5
mass Molecular
.
(a) Ferrous salts are oxidised to ferric salts.
MnO
4
+ 5Fe
2+
+ 8H
+
5Fe
3+
+ Mn
2+
+ 4H
2
O
(b) Iodine is evolved from potassiumiodide.
2MnO
4
+ 10I + 16H
+
2Mn
2+
+ 5I
2
+ 8H
2
O
"manishkumarphysics.in"
25
CHEMISTRY
(c) H
2
S is oxidised to sulphur :
2MnO
4

+ 16H
+
+ 5S
2
2Mn
2+
+ 8H
2
O + 5S
(d) SO
2
is oxidised to H
2
SO
4
:
2MnO
4

+ 5SO
2
+ 2H
2
O 5SO
4
2
+ 2Mn
2+
+ 4H
+
(e) Nitrites are oxidised to nitrates :
2MnO
4

+ 5NO
2

+ 6H
+
2Mn
2+
+ 3H
2
O + 5NO
3

(f) Oxalic acid is oxidised to CO


2
:
This reaction is slow at room temperature, but is rapid at 60C.
Mn(II) ions produced catalyse the reaction; thus the reaction is autocatalytic.
2MnO
4

+ 16H
+
+ 5C
2
O
4
2

C 60
2Mn
2+
+ 8H
2
O + 10CO
2
(g) HCHOis oxidised to HCOOH
2MnO
4

+ 5HCHO + 6H
+
2Mn
2+
+ 5HCOOH + 3H
2
O.
(h) It oxidises hydrogen halides (HCl, HBr or HI) into X
2
(halogen)
2MnO
4

+ 16H
+
+ 10X

2Mn
2+
+ 8H
2
O + 5X
2
(i) H
2
O
2
is oxidised to O
2
.
2MnO
4

+ 6H
+
+ 5H
2
O
2
5O
2
+ Mn
2+
+ 8H
2
O.
Uses :
(i) KMnO
4
is used as an oxidising agent in laboratory and industry.
(ii) Alkaline potassiumpermanganate is called Bayer's reagent. This reagent is used in organic
chemistry for the test of unsaturation. KMnO
4
is used in the manufacture of saccharin,
benzoic acid, acetaldehyde etc.
(iii) KMnO
4
is used in qualitative analysis for detecting halides, sulphites, oxalates, etc.
Example-18 Potassium permanganate acts as an oxidant in neutral, alkaline as well as acidic media. The final
products obtained from it in three conditions are respectively :
(A) MnO
4
2
, Mn
3+
and Mn
2+
(B) MnO
2
, MnO
2
and Mn
2+
(C) MnO
2
, MnO
2
+
and Mn
3+
(D) MnO , MnO
2
+
and Mn
2+
Solution 3e

+ 2H
2
O + MnO
4


MnO
2
+ 4OH

(neutral medium)
e

+MnO
4


MnO
4
2
(dilute alkaline medium)
MnO
4
+ 8H
+
+ 5e

Mn
2+
+ 4H
2
O (acidic medium)
Therefore, (B) option is correct.
[F] POTASSIUMDICHROMATE(K
2
Cr
2
O
7
) :
Preparation :
The chromite ore is roasted with sodiumcarbonate in presence of air in a reverberatory furnace
4FeO. Cr
2
O
3
(chromite ore) + 8Na
2
CO
3
+ 7O
2
air in
Roasting

8Na
2
CrO
4
+ 2Fe
2
O
3
+ 8CO
2
The roasted mass is extracted with water when Na
2
CrO
4
goes into the solution leaving behind
insoluble Fe
2
O
3
. The solution is then treated with calculated amount of H
2
SO
4
.
2Na
2
CrO
4
+ H
2
SO
4
Na
2
Cr
2
O
7
+ Na
2
SO
4
+ H
2
O
The solution is concentrated when less soluble Na
2
SO
4
crystallises out. The solution is further concentrated
when crystals of Na
2
Cr
2
O
7
are obtained. Hot saturated solution of Na
2
Cr
2
O
7
is then treated with KCl when
orange red crystals of K
2
Cr
2
O
7
are obtained on crystallisation.
Na
2
Cr
2
O
7
+ 2KCI K
2
Cr
2
O
7
+ 2 NaCl
"manishkumarphysics.in"
26
CHEMISTRY
K
2
Cr
2
O
7
is preferred over Na
2
Cr
2
O
7
as a primary standardin volumetric estimation because Na
2
Cr
2
O
7
is hygroscopic in nature but K
2
Cr
2
O
7
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 398C.
(b) Chemical :
(i) Effect of heating :
On heating strongly, it decomposes liberating oxygen.
2K
2
Cr
2
O
7
2K
2
CrO
4
+ Cr
2
O
3
+
2
3
O
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.
K
2
Cr
2
O
7
+ 2KOH 2K
2
CrO
4
+ H
2
O
Cr
2
O
7
2
+ 2OH 2CrO
4
2
+ H
2
O
Orange Yellow
2CrO
4
2
+ 2H
+
Cr
2
O
7
2
+ H
2
O
Yellow Orange
Thus CrO
4
2
and Cr
2
O
7
2
exist in equilibrium and are interconvertable by altering the pH of solution.
2CrO
4
2
+ 2H
+
2HCrO
4

Cr
2
O
7
2
+ H
2
O
In alkaline solution, chromate ions are present while in acidic solution, dichromate ions are present.
(ii) K
2
Cr
2
O
7
+ 2H
2
SO
4
(conc. & cold) 2CrO
3
+
(bright orange/red) + 2KHSO
4
+ H
2
O
2K
2
Cr
2
O
7
+ 8H
2
SO
4
(conc. & Hot) 2K
2
SO
4
+ 8H
2
O + 2Cr
2
(SO
4
)
3
+ 3O
2
(iii) Acidified K
2
Cr
2
O
7
solution reacts with H
2
O
2
to give a deep blue solution due to the formation of CrO
5
.
Cr
2
O
7
2
+ 2H
+
+ 4H
2
O
2
2CrO
5
+ 5H
2
O
Blue colour in aqueous solution fades away slowly due to the decomposition of CrO
5
to Cr
3+
ions and
oxygen. In less acidic solution K
2
Cr
2
O
7
and H
2
O
2
give salt which is violet coloured and diamagnetic
due to the formation of [CrO(O
2
)(OH)]

. In alkaline medium with 30% H


2
O
2
, a red-brown K
3
CrO
8
(diperoxo) is formed. It is tetra peroxospecies [Cr(O
2
)
4
]
3
and thus the Cr is in +V oxidation state. In
ammonical solution a dark red-brown compound, (NH
3
)
3
CrO
4
- diperoxo compound with Cr(IV) is
formed.
(iv) Potassium dichromate reacts with hydrochloric acid and evolves chlorine gas.
K
2
Cr
2
O
7
+ 14HCl 2KCl + 2CrCl
3
+ 7H
2
O + 3Cl
2
(v) It acts as a powerful oxidising agent in acidic medium (dilute H
2
SO
4
)
Cr
2
O
7
2
+ 14H
+
+ 6e

2Cr
+3
+ 7H
2
O. (E = 1.33 V)
The oxidation state of Cr changes from + 6 to +3.
(a) Iodine is liberated from potassium iodide :
Cr
2
O
7
2
+ 14H
+
+ 6e

2Cr
3+
+ 7H
2
O
2I

I
2
+ 2e

[3]

Cr
2
O
7
2
+ 14H
+
+ 6I 2Cr
3+
+ 3I
2
+ 7H
2
O
(b) Ferrous salts are oxidised to ferric salts :
6Fe
2+
+ Cr
2
O
7
2
+ 14H
+
6Fe
3+
+ 2Cr
3+
+ 7H
2
O
(c) Sulphites are oxidised to sulphates :
Cr
2
O
7
2
+ 3SO
3
2
+ 8H
+
3SO
4
2
+ 2Cr
3+
+ 4H
2
O
(d) H
2
S is oxidised to sulphur :
Cr
2
O
7
2
+ 3H
2
S + 8H
+
2Cr
3+
+ 7H
2
O + 3S
"manishkumarphysics.in"
27
CHEMISTRY
(e) SO
2
is oxidised to H
2
SO
4
:
Cr
2
O
7
2
+ 3SO
2
+ 2H
+
2Cr
3+
+ 3SO
4
2
+ H
2
O ;
Chrome alum is obtained when acidified K
2
Cr
2
O
7
solution is saturated with SO
2
.
K
2
Cr
2
O
7
+ H
2
SO
4
+ SO
2
+ H
2
O
< C 70 T
K
2
SO
4
. Cr
2
(SO
4
)
3
. 24H
2
O
(f) It oxidises ethylalcohol to acetaldehyde and acetaldehyde to acetic acid
C
2
H
5
OH
] O [
CH
3
CHO
] O [
CH
3
COOH
ethyl alcohol acetaldehyde acetic acid
(g) It also oxidises nitrites to nitrates, arsenites to arsenates, HBr to Br
2
. HI to I
2
, etc.
(h) K
2
Cr
2
O
7
+ 2C (charcoal)
A
Cr
2
O
3
+ K
2
CO
3
+ CO |
(vi) Chromyl chloride test : 4Cl

+ Cr
2
O
7
2
+ 6H
+
2CrO
2
Cl
2
| (deep red) + 3H
2
O
CrO
2
Cl
2
+ 4OH

CrO
4
2
(yellow) + 2Cl

+ 2H
2
O
CrO
4
2
(yellow) + Pb
2+
PbCrO
4
+ (yellow)
(vii) Cr
2
O
7
2
(concentrated solution) + 2Ag
+
Ag
2
Cr
2
O
7
+
(reddish brown)
Ag
2
Cr
2
O
7
+
+ H
2
O

boil
Ag Ag
2
CrO
4
+
+ CrO
4
2
+ 2H
+
.
(viii) Cr
2
O
7
2
+ Ba
2+
+ H
2
O 2BaCrO
4
+
+ 2H
+
As strong acid is produced, the precipitation is only partial. But if NaOH or CH
3
COONa is added,
precipitate becomes quantitative.
Uses :
It is used :
(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) as a cleansing agent for glass ware in the form of chromic acid.
Example-19 An inorganic compound (A) has garnet red prismatic crystals. (A) is moderately soluble in water and
dissolves in cold concentrated H
2
SO
4
to yield red crystals (B). In presence of dilute H
2
SO
4
it
converts a pungent gas (C) into a yellowturbidity (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 KI and
starch in presence of dilute. H
2
SO
4
(A) yields blue colour. (A) and concentrated H
2
SO
4
mixture is
used as a cleansing agent for glassware in the laboratory. Identify (A) and explain the reactions.
Solution As compound (A) has garnet red prismatic crystals which with cold conc. H
2
SO
4
gives red crystals
andasuffocatinggas (SO
2
) turns its solutioninwater intogreencolouredsolution, thereforecompound
(A) may be K
2
Cr
2
O
7
.
K
2
Cr
2
O
7
+ 4H
2
SO
4
+ 3H
2
S

KHSO
4
+ 2 CrO
3
(red crystals) + H
2
O
(A) (B)
K
2
Cr
2
O
7
+ 4H
2
SO
4
+ 3H
2
S

K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 7H
2
O + 3S+ (Yellow)
(C) (D)
K
2
Cr
2
O
7
+ H
2
SO
4
+ 3SO
2

Cr
2
(SO
4
)
3
(Green solution) + K
2
SO
4
+ H
2
O
(E) (F)
K
2
Cr
2
O
7
+ 7H
2
SO
4
+ 6KI

4K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 7H
2
O + 3I
2
I
2
+ Starch

Blue colour
"manishkumarphysics.in"
28
CHEMISTRY
MISCELLANEOUSSOLVEDPROBLEMS(MSPs)
1. Among the following statements choose the true or false statement(s).
(a) K
2
Cr
2
O
7
on heating with charcoal gives metallic potassium and Cr
2
O
3
.
(b) On heating in current of H
2
the crystalline KMnO
4
is converted into KOH and Mn
3
O
4
.
(c) Hydrated ferric chloride on treatment with 2, 2dimethoxypropane gives anhydrous ferric chloride.
Ans. (a) False (b) False (c) True
Sol. (a) K
2
Cr
2
O
7
+ 2C (charcoal)
A
Cr
2
O
3
+ K
2
CO
3
+ CO | .
(b) 2KMnO
4
+ 5H
2

A
2 KOH + 2MnO + 4H
2
O.
(c) FeCl
3
. 6H
2
O+ 6CH
3

3
3
3
OCH
|
CH C
|
OCH

FeCl
3
(anhydrous) + 12CH
3
OH+ 6CH
3
COCH
3
.
2. Acompound (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 K
4
[Fe(CN)
6
].
Identify (A) to (F) and explain the reactions.
Ans. (A) ZnO, (B) Zn(OH)
2
, (C) Na
2
ZnO
2
, (D) Zn, (E) CO, (F) K
2
Zn
3
[Fe(CN)
6
]
2
Sol. Zn(OH)
2
(B)
A
ZnO(A) + H
2
O.
Zn(OH)
2
(B) + + 2OH

[Zn(OH)
4
]
2
(C) (soluble complex).
ZnO (A) + C
A
Zn (D) + CO (E).
Zn(OH)
2
(B) + 4NH
3
[Zn(NH
3
)
4
]
2+
(soluble complex) + 2OH

.
ZnO + 2HCl ZnCl
2
+ H
2
O.
3ZnCl
2
+ 2K
4
[Fe(CN)
6
] K
2
Zn
3
[Fe(CN)
6
]
2
+ (bluish white/white) (F) + 6KCl.
3. 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 NH
4
OH.
Identify the compound (X) and give equations for the reactions (i), (ii) & (iii).
Ans. X=AgNO
3
Sol. 2AgNO
3
(X)
A
2 Ag + 2NO
2
+ O
2
.
AgNO
3
(aq.) + Cl

AgCl + (white) + NO
3

.
AgCl + 2NH
3
[Ag(NH
3
)
2
]
+
(soluble complex).
4. Amongst [TiF
6
]
2
, [CoF
6
]
3
, Cu
2
Cl
2
and [NiCl
4
]
2
[Atomic number ; Ti = 22, Co = 27, Cu = 29, Ni = 28] the
colourless species are :
(A) [TiF
6
]
2
and [Cu
2
Cl
2
] (B) Cu
2
Cl
2
and [NiCl
4
]
2
(C) [TiF
6
]
2
and [CoF
6
]
3
(D) [CoF
6
]
3
and [NiCl
4
]
2
Ans. (A)
Sol. In [TiF
6
]
2
the titanium is in +4 oxidation state having the electronic configuration [Ar]
18
3d
0
4s
0
. Similarly in
Cu
2
Cl
2
the copper is in +1 oxidation state having the electronic configuration [Ar]
18
3d
10
4s
0
. As they do not
have any unpaired electrons for d-d transition, they are therefore colourless.
In [NiCl
4
]
2
the nickel is in +2 oxidation state and electronic configuration is [Ar]
18
3d
8
4s
0
. As it has two
unpaired electrons, so the complex is coloured.
In [CoF
6
]
3
, the cobalt is in +3 oxidation state having electron configuration [Ar] 3d
6
4s
0
. As it has four
unpaired electrons, so the complex is coloured.
"manishkumarphysics.in"
29
CHEMISTRY
5. On the basis of trends in the properties of the 3d-series elements, suggests possible M
2+
aqua ions for use
as reducing agents, and write a balanced chemical equation for the reaction of one of these ions with O
2
in
acidic solution.
Sol. Because oxidation state +2 is most stable for the later elements of 3d-series elements, strong reducing
agents include ions of the metals on the left of the series: such ions include V
2+
(aq) and Cr
2+
(aq) The Fe
2+
(aq) ion is only weakly reducing. The Co
2+
(aq), Ni
2+
(aq), and Cu
2+
(aq) ions are not oxidized in water.
Fe
3+

+ 77 . 0
Fe
2+

44 . 0
Fe
The chemical equation for the oxidation is then
4 Fe
2+
(aq) + O
2
(g) + 4H
+
(aq)

4Fe
3+
(aq) + 2H
2
O ().
6. Match the reactions given in column-I with the characteristic(s) of the reaction products given in
column-II.
Column-I Column-II
(A) TiCl
4

Zn
(p) One of the products is bright orange coloured but
diamagnetic.
(B) FeCl
3

K 573
(q) One of the products is green coloured and paramagnetic.
(C) KMnO
4

K 750
(r) One of the products is violet and paramagnetic.
(D) K
2
Cr
2
O
7
+ H
2
SO
4
(cold & conc.) (s) One of the products exists as dimer.
Ans. [A r] ; [B s ; [C q] ; [D p].
Sol. (A) TiCl
4

Zn
TiCl
3
, violet (one unpaired electron so d-d transition is possible).
(B) 2FeCl
3

K 573
gas dimer..
(C) 2KMnO
4

K 750
K
2
MnO
4
green (one unpaired electron so d-d transition is possible) + MnO
2
+ O
2
.
(D) K
2
Cr
2
O
7
+ 2H
2
SO
4
2CrO
3
bright orange (diamagnetic) + 2KHSO
4
+ H
2
O.
7. Which of the following is true for the species having 3d
4
configuration ?
(A) Cr
2+
is reducing in nature. (B) Mn
3+
is oxidising in nature.
(C) Both (A) and (B) (D) None of these
Sol. Cr
2+
is reducing as its configuration changes from d
4
to d
3
, the latter having a half-filled t
3
2g
energy level of 3d
orbitals in octahedral crystal field spliting. On the other hand, the change from Mn
3+
to Mn
2+
results in the
half-filled (d
5
) configuration which has extra stability.
Therefore, (C) option is correct.
8. Which of the following increasing order of oxidising power is correct for the following species ?
VO
2
+
, MnO
4

, Cr
2
O
7
2
(A) VO
2
+
< Cr
2
O
7
2
< MnO
4

(B) VO
2
+
< MnO
4

< Cr
2
O
7
2
(C) Cr
2
O
7
2
< VO
2
+
< MnO
4

(D) Cr
2
O
7
2
< MnO
4

< VO
2
+
Sol. This is attributed to the increasing stability of the lower species to which they are reduced.
MnO
4

is reduced to Mn
2+
which has stable half filled valence shell electron configuration [3d
5
].
Cr
2
O
7
2
is reduced to Cr
3+
which has half filled t
3
2g
energy level of 3d orbitals in octahedral crystal field spliting
VO
2
+
is reduced to V
3+
which has electronic configuration [Ar]
18
3d
2
4s
0
.
So the order of increasing stability of the reduced species is Mn
2+
> Cr
3+
> V
3+
and, therefore, the increasing
order of oxidising power is VO
2
+
< Cr
2
O
7
2
< MnO
4

.
Therefore, (A) option is correct.
"manishkumarphysics.in"
30
CHEMISTRY
9. 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.
10. When CO
2
is passed into aqueous :
(A) Na
2
CrO
4
solution, its yellow colour changes to orange.
(B) K
2
MnO
4
solution, it disproportionates to KMnO
4
and MnO
2
(C) Na
2
Cr
2
O
7
solution, its orange colour changes to green
(D) KMnO
4
solution, its pink colour changes to green.
Sol. (A) Na
2
CrO
4

+
H
Na
2
Cr
2
O
7
(orange colour)
(B) MnO
4
2

+
H
MnO
4

+ MnO
2
, in neutral or acidic medium
(C) False - In acidic medium no colour change takes place.
(D) MnO
4

+ e



OH
MnO
4
2
; in strong alkaline medium pink colour of KMnO
4
changes to green.
Therefore, (A,B) options are correct.
11. Which of the following statement(s) is (are) not correct with reference to ferrous and ferric ions
(A) Fe
3+
gives brown colour with potassiumferricyanide
(B) Fe
2+
gives blue precipitate with potassium ferricyanide
(C) Fe
3+
gives red colour with potassium sulphocyanide
(D) Fe
2+
givesbrowncolour withpotassiumsulphocyanide
Sol. Fe
3+
produces red colouration with KSCN but Fe
2+
does not give brown colour with KSCN.
Therefore, (D) option is correct.
12. STATEMENT-1 : Ammonical silver nitrate converts glucose to gluconic acid and metallic silver is precipitated.
STATEMENT-2 : Glucose acts as a weak reducing agent.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
Sol. (A) Ag
2
O + C
6
H
12
O
6
2Ag + C
6
H
12
O
7
.
13. STATEMENT-1 : The number of unpaired electrons in the following gaseous ions :
Mn
3+
, Cr
3+
, V
3+
and Ti
3+
are 4, 3, 2 and 1 respectively.
STATEMENT-2 : Cr
3+
is most stable in aqueous solution among these ions.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
Sol. (B) Mn
3+
= [Ar]
18
3d
4
, Cr
+3
= [Ar]
18
3d
3
, V
3+
= [Ar]
18
3d
2
, Ti
3+
= [Ar]
18
3d
1
Cr
3+
is most stable in aqueous solution because it has half filled t
3
2g
energy level of 3d orbitals in
octahedral crystal field spliting and according to crystal field theory (CFT) it has highest value of
CFSE i.e. 1.2 A
O
.
"manishkumarphysics.in"
31
CHEMISTRY
14. S
1
: Interstitial compounds have high melting points, higher than those of pure metals.
S
2
: Permanganate titrations in presence of hydrochloric acid are unsatisfactory.
S
3
: KMnO
4
does not act as an oxidising agent in strong alkaline medium.
S
4
: KMnO
4
on heating in a current of H
2
gives MnO.
(A) T T F T (B) T F F T (C) T F T T (D) F F T F
Sol. S
1
: Due to strong interatomic forces.
S
2
: Some of the hydrochloric acid is oxidised to chlorine and thus we get less volume of KMnO
4
than the
actual one.
S
3
: MnO
4

+ e



OH
MnO
4
2
S
4
: 2KMnO
4
+ 5H
2

2KOH + 2MnO + H
2
O.
Therefore, (A) option is correct.
15. Match the reactions in Column I with nature of the reactions/type of the products in Column II.
Column I Column II
(A) AgNO
3
(aq) + I
2
(excess) + H
2
O (p) Disproportionation
(B) K
2
MnO
4
(aq) + CO
2
(g) (q) Comproportionation
(C) Na
2
Cr
2
O
7
+ C
A
(r) Redox
(D) CuCl
2
(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)
Sol. (A) 5AgNO
3
(aq) + 3
0
I
2
(excess) + 3H
2
O
V
3
HIO
+
+
1
AgI 5 + 5HNO
3
So it is redox and disproportionation reaction. AgI insoluble in water.
(B)
VI
4 2
MnO K 3
+
(aq) + 2CO
2
(g)
VII
4
KMnO 2
+
+
IV
2
MnO
+
+ 2K
2
CO
3
So it is redox and disproportionation reaction. MnO
2
insoluble in water.
(C)
0
C 2
+
VI
7 2 2
O Cr Na
+

A
III
3 2
O Cr
+
+
IV
3 2
CO Na
+
+
|
+II
CO
So it is redox reaction. Cr
2
O
3
(green pigment) is insoluble in water.
(D)
II
2
CuCl
+
(aq) +
0
Cu
(s)
I
2 2
Cl Cu
+
(s)
So it is redox and comproportionation reaction. Cu
2
Cl
2
is insoluble in water.