d-BLOCK ELEMENTS (Inorganic Chemistry)

TRANSITION ELEMENTS (2) The lesser number of oxidation states at the extreme ends
Definition: They one often called 'transition elements' stems from either too few electrons to lose or share (Sc, Ti)
because their position in the periodic table is between s- or too many d electrons (hence fewer orbitals available in
block and p-block elements Typically, the transition which to share electrons with others) for higher valence (
elements have an incompletely filled d-level, are not Cu, Zn).
considered as transition elements but they are d-block (3) Thus, early in the series scandium(II) is virtually
elements. Since Zn group has d10 configuration in their unknown and titanium (IV) is more stable than Ti(III) or
ground state as well as in stable oxidation state, they are not Ti(II).
considered as transition elements but they are d-block (4) At the other end, the only oxidation state of zinc is +2 (no
elements. d electrons are involved).
(5) The maximum oxidation states of reasonable stability
correspond in value to the sum of the s and d electrons upto
manganese (TiIV O2 , V V O2 + , Cr VI O4 2− , MnVII O4− )followed by
a rather abrupt decrease in stability of higher oxidation
states, so that the typical species to follow are
FeII,III , CoII,III , NiII , CuI,II , ZnII .
(6) The variability of oxidation states, a characteristic of
transition elements, arises out of incomplete filling of d
orbitals in such a way that their oxidation states differ from
each other by unity, e.g., V II , V III , V IV , V V .
(7) This is in contrast with the variability of oxidation states
of non transition elements where oxidation states normally
General Characteristics: differ by a unit of two.
(i) Metallic character: They are all metal and good (8) An interesting feature in the variability of oxidation
conductor of heat & electricity states of the d-block elements is noticed among the groups
(ii) Electronic configuration: (n − 1)d1−10 ns1−2 (groups 4 through 10 ).
(9) In group 6, Mo(VI) and W(VI) are found to be more stable
than Cr(VI). Thus Cr(VI) in the form of dichromate in acidic
medium is a strong oxidising agent, whereas MoO3 and WO3
(iii) M.P. are not.
(10) Low oxidation states are found when a complex
compound has ligands capable of π-acceptor character in
(iv) Variation in atomic radius: addition to the σ-bonding. For example, in Ni(CO)4 and
Fe(CO)5 , the oxidation state of nickel and iron is zero.
(11) As the oxidation number of a metal increases, ionic
character decreases. In the case of Mn, Mn2 O7 is a covalent
green oil. Even CrO3 and V2 O5 have low melting points. In
(v) Ionisation energy: these higher oxides, the acidic character is predominant.
Thus, Mn2 O7 gives HMnO4 and CrO3 gives H2 CrO4 and
1st , 2nd , 3rd , IE, s are increasing from left to right for 1st
H2 Cr2 O7 . V2 O5 is, however, amphoteric though mainly acidic
Transition series, but not regularly.
and it gives VO3− 4 as well as VO
2+
salts. In vanadium there is
For 2nd IECr > Fe > Mn and Cu > Zn
gradual change from the basic V2 O3 to less basic V2 O4 and to
For 3rd IEMn > Cr > Fe and Z has highest.
amphoteric V2 O5 . V2 O4 dissolves in acids to give VO2+ salts.
Similarly, V2 O5 reacts with alkalies as well as acids to give
4 and VO4 respectively. The well characterised CrO is
VO3− +

basic but Cr2 O3 is amphoteric.

VARIABLE OXIDATION STATES POSSIBLE:

(1) The elements which give the greatest number of
oxidation states occur in or near the middle of the series.
Manganese, for example, exhibits all the oxidation states
from +2 to +7 .

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Oxidation state of the 𝐈 st transition series Most common (9) Beyond Group 7, no higher oxides of Fe above Fe2 O3 , are
ones are in bole types: known, although ferrates (VI) (FeO4 )2− , are formed in
alkaline media but they readily decompose to Fe2 O3 and O2 .
(10) Besides the oxides, oxocations stabilise V v as VO+ 2,V
IV

as VO and Ti as TiO
2+ IV 2+

(11) The ability of oxygen to stabilise these high oxidation

states exceeds that of fluorine. Thus the highest Mn fluoride
is MnF4 whereas the highest oxide is Mn2 O7 . The ability of
oxygen to form multiple bonds to metals explains its
superiority.
(12) In the covalent oxide Mn2 O7 , each Mn is tetrahedrally
surrounded by O 's including a
Mn-O-Mn bridge.
(13) The tetrahedral [MO4 ]n ions are known for
V V , Cr Vl , MnV , MnVI and MnVII . FORMATION OF
Trends in stability of higher oxidation state: COLOURED ION:
(1) Table shows the stable halides of the 3 d series of Colour: (aquated)
transition metals. The highest oxidation numbers are Ta4+ ⟶ colourless Sc 3+ ⟶ colourless
achieved in TiX 4 (tetrahalides), VF5 and CrF6 . The +7 state V ⟶ blue
4+
Ti3+ ⟶ purple
for Mn is not represented in simple halides but MnO3 F is V ⟶ violet
2+
V 3+ ⟶ green
known, and beyond Mn no metal has a trihalide except FeX 3 Cr ⟶ green
3+
Cr 2+ ⟶ blue
and CoF3 . Mn ⟶ light pink
2+
Mn3+ ⟶ violet
(2) The ability of fluorine to stabilise the highest oxidation Fe ⟶ yellow
3+
Fe2+ ⟶ light green
state is due to either higher lattice energy as in the case of Ni ⟶ green
2+
Co2+ ⟶ pink
CoF3 , or higher bond enthalpy terms for the higher covalent Zn ⟶ colourless
2+
Cu2+ ⟶ blue
compounds, e.g., VF5 and CrF6 . CATALYTIC PROPERTIES
(3) Although V V is represented only by VF5 , the other halides, (1) The transition metals and their compounds are known
however, undergo hydrolysis to give oxohalides, VOX3 . for their catalytic activity. This activity is ascribed to their
(4) Another feature of fluorides is their instability in the low ability to adopt multiple oxidation states and to form
oxidation states complexes. Vanadium (V) oxide (in Contact Process), finely
e.g., VX 2 (X = CI, Br or I) divided iron (in Haber's Process), and nickel (in Catalytic
Formulas of halides of 𝟑𝐝-metals Hydrogenation) are some of the examples.
(2) Catalysts at a solid surface involve the formation of bonds
between reactant molecules and atoms of the surface of the
catalyst (first row transition metals utilise 3 d and 4 s
electrons for bonding).
(3) This has the effect of increasing the concentration of the
reactants at the catalyst surface and also weakening of the
bonds in the reacting molecules (the activation energy is
lowering).
Key : X = F → I; X I = F → Br; X II = F → Cl; X III = Cl → I (4) Also because the transition metal ions can change their
and the same applies to CuX. On the other hand, all Cu(II) oxidation states, they become more effective as catalysts. For
halides are known except the iodide. example, iron(III) catalyses the reaction between iodide and
In this case, Cu2+ oxidises I − to I2 : persulphateions.
2Cu2+ + 4I − → Cu2 I2 ( s) + I2 2I − + S2 O8 2− → I2 + 2SO4 2−
(5) However, many copper (I) compounds are unstable in An explanation of this catalytic action can be given as:
aqueous solution and undergo disproportionation. 2Fe3+ + 2I − → 2Fe2+ + I2
2Cu+ → Cu2+ + Cu 2Fe2+ + S2 O2− 8 → 2Fe
3+
+ 2SO4 2−
(6) The stability of Cu2+ (aq) rather than Cu+ (aq) is due to
the much more negative ΔHyd H Θ of Cu2+ (aq) than Cu+ ,
which more than compensates for the second ionisation
enthalpy of Cu.
(7) The ability of oxygen to stabilise the highest oxidation
state is demonstrated in the oxides.
(8) The highest oxidation number in the oxides coincides
with the group number and is attained in Sc2 O3 to Mn2 O7 .

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fusion]
Then, 2Na 2 CrO4 + H2 SO4 ⟶ Na 2 SO4 ↓ +Na 2 Cr2 O7 + H2 O
Conc.
Its solubility Hence, suitable temp. is to be
Upto 32∘ C increases } Employed to crystallise out
And then decreases Na 2 SO4 first.
Then Na 2 Cr2 O7 is crystallised out as Na 2 Cr2 O7 2H2 O on
evaporation. (red crystal)
How to get 𝐊 𝟐 𝐂𝐫𝟐 𝐎𝟕 :

Hot conc.
NaCl crystallises out first and filtered off. Then K 2 Cr2 O7
crystallised out on cooling
The chromates and dichromates are interconvertible in
aqueous solution depending upon pH of the solution.
The oxidation state of chromium in chromate and
dichromate is the same.
Formation of Interstitial Compounds 2CrO2− + 2−
4 + 2H → Cr2 O7 + H2 O
Interstitial compounds are those which are formed when Cr2 O7 + 2OH → 2CrO2−
2− −
4 + H2 O
small atoms like H, C or N are trapped inside the crystal The structures of chromate ion, CrO4 2− and the dichromate
lattices of metals. The principal physical and chemical ion, Cr2 O7 2− are shown below. The chromate ion is
characteristics of these compounds are as follows: tetrahedral whereas the dichromate ion consists of two
(i) They have high melting points, higher than those of pure tetrahedra sharing one corner with Cr − O − Cr bond angle
metals. of 126∘ . Sodium and potassium dichromates are strong
(ii) They are very hard, some borides approach diamond in oxidising agents; the sodium salt has a greater solubility in
hardness. water and is extensively used as an oxidising agent in organic
(iii) They retain metallic conductivity. chemistry. Potassium dichromate is used as a primary
(iv) They are chemically inert. standard in volumetric analysis. In acidic solution, its
Alloy Formation oxidising action can be represented as follows:
An alloy is a blend of metals prepared by mixing the Cr2 O2− + − 3+
+ 7H2 O(E Θ = 1.33 V)
7 + 14H + 6e → 2Cr
components. Alloys may be homogeneous solid solutions
in which the atoms of one metal are distributed randomly
among the atoms of the other. Such alloys are formed by
atoms with metallic radii that are within about 15 percent of
each other.
Because of similar radii and other characteristics of
transition metals, alloys are readily formed by these metals.
Thus, acidified potassium dichromate will oxidise iodides to
The alloys so formed are hard and have often high melting
iodine, sulphides to sulphur, tin (II) to tin (IV) and iron(II)
points. The best known are ferrous alloys: chromium,
salts to iron(III). The half-reactions are noted below:
vanadium, tungsten, molybdenum and manganese are used
6I − → 3I2 + 6e− ; 3Sn2+ → 3Sn4+ + 6e−
for the production of a variety of steels and stainless steel.
Alloys of transition metals with non transition metals such as 3H2 S → 6H + 3 S + 6e ; 6Fe2+ → 6Fe3+ + 6e−
+ −

brass (copper-zinc) and bronze (copper-tin), are also of The full ionic equation may be obtained by adding the half-
considerable industrial importance. reaction for potassium dichromate to the half-reaction for
CHROMATE – DICHROMATE the reducing agent, for e.g.,
Cr2 O2− +
7 + 14H + 6Fe
2+
→ 2Cr 3+ + 6Fe3+ + 7H2 O
Similarities between hexavalent Cr& S-compounds:
(i) SO3 &CrO3 ⟶ both acidic.
(ii) S ⟶ SO2− 2− 2−
4 , S2 O7 , Cr ⟶ CrO4 , Cr2 O7
2−

(iii) CrO4−2 &SO2−4 are isomorphous

OH−
(iv) SO2 Cl2 &CrO2 Cl2 ⟶ SO2−
4 &CrO4 respectively.
2−
Preparation: OH−
(v) SO3 Cl− &CrO3 Cl− ⟶ SO2−
4 &CrO4
2−

(vi) CrO3 &β(SO3 ) has same structure

(chromite ore)
[Lime (CaO) added with Na 2 CO3 which keeps the mass
porous so that air has access to all parts and prevents

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1
But in the above method of Mn is lost as MnO2 but when
3
oxidised either by Cl2 or by O3 2 K 2 MnO4 + Cl2 ⟶
2KMnO4 + 2KCl [Unwanted MnO2 does not form]
OR
2 K 2 MnO4 + O3 + H2 O ⟶ 2KMnO4 + 2KOH + O2
Q. In laboratory 𝐊 𝟐 𝐂𝐫𝟐 𝐎𝟕 is used mainly not
OR
𝐍𝐚𝟐 𝐂𝐫𝟐 𝐎𝟕 . Why?
Sol. Na 2 Cr2 O7 is deliquescent enough and changes its
concentration and can not be taken as primary
standard solution whereas K 2 Cr2 O7 has no water of
crystallisation and not deliquescent. Oxidising Prop. of 𝐊𝐌𝐧𝐎𝟒 : (in acidic medium)
Q. How to standardise Na2S2O3 solution in (i) MnO4− + Fe+2 + H + ⟶ Fe+3 + Mn+2 + H2 O
iodometry? (ii) MnO4− + Γ + H + ⟶ Mn+2 + I2 + H2 O
Sol. K 2 Cr2 O7 is primary standard ⇒ strength is known by (iii) MnO4− + H2 O2 + H + ⟶ Mn+2 + O2 + H2 O
H⊕
weighing the salt in chemical balance and dissolving (iv) MnO4− + SO2 ⟶ Mn+2 + H2 SO4
in measured amount of water. (v) MnO4− + NO2− + H + ⟶ Mn+2 + NO3− + H2 O
Then in acidic solution add. KI (vi) MnO4− + H2 C2 O4 + H + ⟶ Mn+2 + CO2 + H2 O
Cr2 O2− +
7 + 14H + 6 F ⟶ 2Cr
3+
+ 3I2 + 7H2 O (vii) MnO4− + H2 S ⟶ Mn2+ + S ↓ +H2 O
This I2 is liberated can be estimated with S2 O3 2− . (viii) MnO4− + S2 O2−
3 ⟶ Mn
2+
+ S ↓ +SO2− 4
MANAGANATE & PERMANGANATE (1) It is not a primary standard since it is difficult to get it in
PREPARATION OF MANGANATE (MnO2− 4 ) :- a high degree of purity and free from traces of MnO2 .
(2) It is slowly reduced to MnO2 especially in presence of
light or acid
4MnO4− + 4H + ⟶ 4MnO2 + 2H2 O + 3O2
Hence it should be kept in dark bottles and standardise just
before use.
(ix) 2KMnO4 + 16HCl ⟶ 2KCl + 5Cl2 + 8H2 O + 2MnCl2
Note: Permanganate titrations in presence of
hydrochloric acid are unsatisfactory since hydrochloric
acid is oxidised to chlorine.
Oxidising Prop. of 𝐊𝐌𝐧𝐎𝟒 in neutral or faintly alkaline
solution.
2MnO4− + 2OH − ⟶ 2MnO2− 4 + H2 O + O. Then 2MnO4
2−

+ 2H2 O ⟶ 2MnO2 + 4OH − + 2O

(i) 2KMnO4 + H2 O + KI ⟶ 2MnO2 + 2KOH + KIO3
(ii) 2KMnO4 + 3HCO2 K ⟶ 2MnO2 + KHCO3 + 2 K 2 CO3 +
H2 O
(iii) 2KMnO4 + 3H2 O2 ⟶ 2KOH + 2MnO2 + 2H2 O + 3O2
(iv) Thiosulphate is oxidised almost quantitatively to
sulphate:
8MnO4− + 3 S2 O2− 2−
3 + H2 O ⟶ 8MnO2 + 6SO4 + 2OH
−

Oxidising Prop. in neutral or weakly acidic solution:

In presence of KClO3 &KNO3 the above reaction is more faster in presence Zn+2 or ZnO
because these two on decomposition provides O2 easily. (i) 2KMnO4 + 3MnSO4 + 2H2 O ⟶ 5MnO2 +
Manganate is also obtained when KMnO4 is boiled with KOH. K 2 SO4 + 2H2 SO4
boiled or MnO4− + Mn+2 + 2H2 O ⟶ 5MnO2 + 4H +
4KMnO4 + 4KOH ⟶ 4 K 2 MnO4 + 2H2 O + O2 In absence of Zn+2 ions, some of the Mn+2 ion may escape,
Properties: The above green solution is quite stable in alkali, oxidation through the formation of insoluble
but in pure water and in presence of acids, depositing
MnII [MnIV O3 ] manganous permanganite.
MnO2 and giving a purple solution of permanganate.
Uses of 𝐊𝐌𝐧𝐎𝟒 :
3 K 2 MnO4 + 2H2 O ⟶ 2KMnO4 + MnO2 ↓ +4KOH
0 Besides its use in analytical chemistry, potassium
prob. : EMnO 2 −MnO = 2.26 V; EMnO2 /MnO− = 0.56 V
2 4 permanganate is used as a best oxidant in preparative
2 2
Prove that MnO2−4 will disproportionate in acidic medium. organic chemistry. Its uses for the bleaching of wool, cotton,
Conversion of 𝐌𝐧𝐎𝟐− 𝟒 to 𝐌𝐧𝐎𝟒
−
silk and other textile fibres and for the decolourisation of oils
3 K 2 MnO4 + 2H2 SO4 ⟶ 2KMnO4 + MnO2 are also dependent on its strong oxidising power.
↓ +2 K 2 SO4 + 2H2 O In laboratory conversion of Mn+2 to MnO4 − is done by :
3 K 2 MnO4 + 2H2 O + 4CO2 ⟶ 2KMnO4 + MnO2 + 4KHCO3 (i) PbO2 (ii) Pb3 O4 + HNO3 (iii) Pb2 O3 + HNO3

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(iv) NaBiO3 /H + (v) (NH4 )2 S2 O8 /H + (vi) KIO4 /H + AgO supposed to be paramagnetic due to d9 configuration.
Heating effect: But actually it is diamagnetic and existsas Ag I [Ag III O2 ]
Reaction involved in developer :
K 2 FeII (C2 O4 )2 + AgBr ⟶ KFeIII (C2 O4 )2 + Ag ↓ +KBr
ZINC COMPOUNDS
𝐙𝐧𝐎
It is called as phillospher's wool due to its wooly flock type
SILVER AND ITS COMPOUND
appearance
(I)
Preparation:
[1] 2 Zn + O2 ⟶ 2ZnO
[2] Calcination of ZnCO3 or Zn(NO3 )2 or Zn(OH)2
Purest 𝐙𝐧𝐎: 4ZnSO4 + 4Na 2 CO3 + 3H2 O ⟶ ZnCO3 ⋅
3Zn(OH)2 ↓ +4Na 2 SO4 + 3CO2

Hence in presence of O2 .
Ag reacts with dil. HCl
4Ag + 4HCl + O2 ⟶ 4AgCl ↓ +2H2 O
In the same way in presence of O2 , Ag complexes with
NaCN/KCN. Properties:
Δ
4Ag + 8KCN + 2H2 O + O2 ⟶ 4 K[Ag(CN)2] + 4KOH [1] ZnO( cold ) ⇄ ZnO( hot )
AgNO3 white yellow
Preparation: Reaction of Ag with dilute HNO3 or conc. [2] It is insoluble in water
HNO3 . [3] It sublimes at 400∘ C
Properties: [4] It is amphoteric oxide , react with acid & base both.
(i) It is called as lunar caustic because in contact with skin it ZnO + 2HCl ⟶ ZnCl2 + H2 O
produces burning sensation like that of caustic soda with
ZnO + H2 SO4 ⟶ ZnSO4 + H2 O
the formation of finely divided silver (black colour)
ZnO + 2NaOH ⟶ Na 2 ZnO2 + H2 O
(ii) Thermal decomposition :
[5] ZnO ⟶ Zn by H2 &C
(iii) Props. of AgNO3 >400∘ C
AgNO3 + 3I2 + 3H2 O ⟶ 5AgI + AgIO3 + 6HNO3 ZnO + H2 ⟶ Zn + H2 O
(excess) ZnO + C ⟶ Zn + CO
Δ [6] It forms Rinmann's green with Co(NO3 )2
(iv) Ag 2 SO4 ⟶ 2Ag + SO2 + O2
2Co(NO3 )2 ⟶ 2CoO + 4NO2 + O2
AgCl, AgBr, AgI (but not Ag 2 S ) are soluble in Na 2 S2 O3
forming [Ag(S2 O3 )2 ]−3 complexes CoO + ZnO ⟶ CoZnO2 or CoO ⋅ ZnO
KBr Rinmann's green
(vii) AgBr + AgNO3 ⟶ AgBr ↓ +KNO3 Uses: (1) As white pigment, it is superior than white lead
Pale yellow because it does not turn into black
ppt. (2) Rinmann's green is used as green pigment
212∘ C
Heating effect: 2AgNO3 ⟶ 2AgNO2 + O2 (3) It is used as zinc ointment in medicine
500∘ C
2AgNO2 ⟶ 2Ag + 2NO + O2 𝐙𝐧𝐂𝐥𝟐
(viii) Preparation: ZnO + 2HCl ⟶ ZnCl2 + H2 O

ZnCO 3 + 2HCl ⟶ ZnCl2 + H2 O } It crystallises as ZnCl2 2H2 O

Zn(OH)2 + 2HCl ⟶ ZnCl + 2H2 O
Anh. ZnCl2 cannot be made by heating ZnCl2 ⋅ 2H2 O because
Δ
ZnCl2 ⋅ 2H2 O ⟶ Zn(OH)Cl + HCl + H2 O
Δ
Zn(OH)Cl ⟶ ZnO + HCl
To get anh. ZnCl2 : Zn + Cl2 ⟶ ZnCl2
Zn + 2HCl( dry ) ⟶ ZnCl2 + H2
Ag 2 O + H2 O2 ⟶ 2Ag + H2 O + O2 or Zn + HgCl2 ⟶ ZnCl2 + Hg
K 2 S2 O8 + 2AgNO3 + 2H2 O ⟶ 2AgO + 2KHSO4 + 2HNO3

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Properties: (ii) dil. solution in water is blue in colour due to formation of

(i) It is deliquescent white solid (when anhydrous) [Cu(H2 O)4 ]2+ complex.
(ii) ZnCl2 + H2 S ⟶ ZnS (iii) conc. HCl or KCl added to dil. solution of CuCl2 the colour
excess
“ +NaOH ⟶ Zn(OH)2 ⟶ Na 2 [Zn(OH)4 ] changes into yellow, owing to the formation of [CuCl4 ]2−
excess (iv) The conc. aq. solution is green in colour having the two
“ +NH4 OH ⟶ Zn(OH)2 ⟶ [Zn(NH)4 ]2+ complex ions in equilibrium
Uses: 2[Cu(H2 O)4 ]Cl2 ⇌ [Cu(H2 O)4 ]2+ + [CuCl4 ]2− + 4H2 O
[1] Used for impregnating timber to prevent destruction by (v) CuCl2 ⟶ CuCl by no. of reagents
insects Δ
[2] As dehydrating agent when anhydrous (a) CuCl2 + Cu-turnings ⟶ 2CuCl
[3] ZnO ⋅ ZnCl2 used in dental filling (b) 2CuCl2 + H2 SO3 + H2 O ⟶ 2CuCl + 2HCl + 2H2 SO4
𝐙𝐧𝐒𝐎4 (c) 2CuCl2 + Zn/HCl ⟶ 2CuCl + ZnCl2
𝐏𝐫𝐞𝐩𝐚𝐫𝐚𝐭𝐢𝐨𝐧: ⎯→Zn + dil H2 SO4 ⟶ ZnSO4 + H2 (d) CuCl2 + SnCl2 ⟶ CuCl + SnCl4
ZnO + dil H2 SO4 ⟶ ZnSO4 + H2 O CuF3 ⋅ 2H2 O ⟶ light blue
ZnCO3 + dil H2 SO4 ⟶ ZnSO4 + H2 O + CO2 CuCl2 ⋅ 2H2 O ⟶ green
Zn2O2 ⟶ ZnSO CuBr2 ⟶ almost black
3 } Parallel reaction Anh. CuCl2 is dark brown mass obtained
ZnS + O2 ⟶ ZnO + SO2 { By heating CuCl2 ⋅ 2H2 O at 150∘ C in presence
2
ZnS + 4O3 ⟶ ZnSO4 4O2 of HCl vap.
150∘ C
Properties: CuI2 does not exit CuCl2 ⋅ 2H2 O ⟶ CuCl2 + 2H2 O
39−70∘ C >70∘ C HCl gas
ZnSO4 ⋅ 7H2 O ⟶ ZnSO4 ⋅ 6H2 O ⟶ ZnSO4 Preparation: → CuSO4
>280∘ C
⋅ H2 O ⟶ ZnSO2 CuO + H2 SO4 (dil) ⟶ CuSO4 + H2 O
Cu(OH)2 + H2 SO4 (dil) ⟶ CuSO4 + 2H2 O
Cu(OH)2 ⋅ CuCO3 + H2 SO4 (dil) → CuSO4 + 3H2 O + CO2
1
Cu + H2 SO4 + O2 ⟶ CuSO4 + H2 O [Commercial scale]
2
(Scrap)
Uses: [1] in eye lotion Cu + dil. H2 SO4 ⟶ no reaction {Cu is a below H in
[2] Lithophone making (ZnS + BaSO4 ) as white pigment electrochemical series }
COPPER COMPOUNDS Properties: → (i) It is crystallised as CuSO4 ⋅ 5H2 O
𝐂𝐮𝐎
Δ
Preparation: (i) CuCO3 ⋅ Cu(OH)2 ⟶ 2CuO + H2 O + CO2
(Commercial process )
Malachite Green
(native Cu-carbonate)
1
(ii) 2Cu + O2 ⟶ 2CuO&Cu2 O + O2 ⟶ 2CuO
2
Δ
(iii) Cu(OH)2 ⟶ CuO + H2 O
250∘ C
(iv) 2Cu(NO3 )2 ⟶ 2CuO + 4NO2 + O2 (iii) Revision with all others reagent
Properties: (i) CuO is insoluble in water IRON COMPOUNDS
(ii) Readily dissolves in dil. Acids 𝐅𝐞𝐒𝐎𝟒 ⋅ 𝟕𝐇𝟐 𝐎
CuO + H2 SO4 ⟶ CuSO4 + H2 O Preparation: → (i) Scrap Fe + H2 SO4 ⟶ FeSO4 + H2 ↑
HCl ⟶ CuCl2 (dil.)
HNO3 ⟶ Cu(NO3 )2 (ii) From Kipp's waste
(iii) It decomposes when, heated above 1100∘ C FeS + H2 SO4 ( dil) ⟶ FeSO4 + H2 S ↑
7
4CuO ⟶ 2Cu2 O + O2 (iii) FeS2 + 2H2 O + O2 ⟶ FeSO4 + H2 SO4
2
(iv) CuO is reduced to Cu by H2 or C under hot Properties: → (i) It undergoes aerial oxidation forming basic
condition ferric sulphate
CuO + C ⟶ Cu + CO ↑ 4FeSO4 + H2 O + O2 ⟶ 4Fe(OH)SO4
CuO + H2 ⟶ Cu + H2 O ↑ 300∘ C temp.
𝐂𝐮𝐂𝐥𝟐 (ii) FeSO4 ⋅ 7H2 O ⟶ FeSO4 ⟶ Fe2 O3 + SO2 + SO3
high
Preparation: → CuO + 2HCl (conc.) ⟶ CuCl2 + H2 O [Link]
Cu(OH)2 ⋅ CuCO3 + 4HCl ⟶ 2CuCl2 + 3H2 O + CO2 (iii) Aq. solution is acidic due to hydrolysis
Properties: → (i) It is crystallised as CuCl2 ⋅ 2H2 O of FeSO4 + 2H2 OlFe(OH)2 + H2 SO4
Emerald green colour weak base
(iv) It is a reducing agent
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(a) Fe2+ + MnO4− + H + ⟶ Fe3+ + Mn2+ + H2 O

(b) Fe2+ + CrO2− +
7 + H ⟶ Fe
3+
+ Cr 3+ + H2 O
(c) Au + Fe ⟶ Au + Fe
3+ 2+ 3+

(d) Fe2+ + HgCl2 ⟶ Hg 2 Cl2 ↓ +Fe3+

white ppt.
(v) It forms double salt. Example (NH4 )2 SO4 ⋅ FeSO4 ⋅ 6H2 O
FeO(Black)
Δ
Preparation: FeC2 O4 FeO + CO + CO2
in absence of air
Properties: It is stable at high temperature and on cooling
slowly disproportionates into Fe3 O4 and iron
4FeO ⟶ Fe3 O4 + Fe
𝐅𝐞𝐂𝐥𝟐
heated in
Preparation: Fe + 2HCl FeCl2 + H2
a currenmt of HCl
OR
Δ
2FeCl3 + H2 ⟶ 2FeCl2 + 2HCl
Properties: → (i) It is deliquescent in air like FeCl3
(ii) It is soluble in water, alcohol and ether also because it is
suffici Covalent in nature
(iii) It volatilises at about 1000∘ C and vapour density
indicates the presen of Fe2 Cl4 . Above 1300∘ C density
becomes normal
(iv) It oxidises on heating in air
12FeCl2 + 3O2 ⟶ 2Fe2 O3 + 8FeCl3
(v) H2 evolves on heating in steam
3FeCl2 + 4H2 O ⟶ Fe3 O4 + 6HCl + H2
(vi) It can exist as different hydrated form
FeCl2 ⋅ 2H2 O ⟶ colourless
FeCl2 ⋅ 4H2 O ⟶ pale green
FeCl2 ⋅ 6H2 O ⟶ green

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EXERCISE-I (C) X = [Cu(H2 O)4 ]+ , Y = I2

Select one or more than one correct options. (D) X = [Cu(H2 O)5 ]2+ , Y = I2
1. (T) imparts violet colour in the flame test
10. (NH4 )2 Cr2 O7 (Ammonium dichromate) is used in
fireworks. The green coloured powder blown in air
NH3 soln.
(W)Red ppt. ⟶ (X) is
dil HCl (A) Cr2 O3 (B) CrO2
(W)Red ppt. ⟶ (Y)white ppt. (C) Cr2 O4 (D) CrO3
NaOH
Δ 11. The d-block element which is a liquid at room
(U) ⟶ (Z)gas (gives white fumes with HCl ) temperature, having high specific heat, less reactivity
sublimes on heating than hydrogen and its chloride (MX2 ) is volatile on
Identify (𝐓) to (𝐙). heating is
(A) T = KMnO4 , U = HCl, V = Cl2 , W = HgI2 , (A) Cu (B) Hg (C) Ce (D) Pm
X = Hg(NH2 )NO3 , Y = Hg 2 Cl2 , Z = N2
12. Coinage metals show the properties of
(B) (B) T = K 2 Cr2 O7 , U = NH4 Cl, V = CrO2 Cl2 ,
(A) typical elements
W = Ag 2 CrO4 , X = [Ag(NH3 )2 ]+ , Y = AgCl, Z = NH3
(B) normal elements
(C) T = K 2 CrO4 , U = KCl, V = CrO2 Cl2 , W = HgI2 , X =
(C) inner-transition elements
Na 2 CrO4 , Y = BaCO3 , Z = NH4 Cl
(D) transition element
(D) T = K 2 MnO4 , U = NaCl, V = CrO3 , W =
AgNO2 , X = (NH4 )2 CrO4 , Y = CaCO3 , Z = SO2 13. Iron becomes passive by…………. due to formation
of……………..
2. The number of moles of acidified KMnO4 required to
(A) dil. HCl, Fe2 O3
convert one mole of sulphite ion into sulphate ion is
(B) 80% conc. HNO3 , Fe3 O4
(A) 2/5 (B) 3/5 (C) 4/5 (D) 1
(C) conc. H2 SO4 , Fe3 O4
3.
Fe+Mo
N2 ( g) + 3H2 ( g) ⇌ 2NH3 ( g); Haber's process, (D) conc. HCl, Fe3 O4
Mo is used as 14. Bayer's reagent used to detect olefinic double bond is
(A) a catalyst (A) acidified KMnO4
(B) a catalytic promoter (B) aqueous KMnO4
(C) an oxidising agent (C) 1% alkaline KMnO4 solution
(D) as a catalytic poison (D) KMnO4 in benzene
4. CrO3 dissolves in aqueous NaOH to give 15. The transition metal used in X-rays tube is
(A) Cr2 O2−
7 (B) CrO4 2− (A) Mo (B) Ta (C) Tc (D) Pm
(C) Cr(OH)3 (D) Cr(OH)2
5. An ornamental of gold having 75% of gold, it is of 16.
carat.
(A) 18 (B) 16 (C) 24 (D) 20
6. Solution of MnO4− is purple-coloured due to
(A) d-d-transition
(B) charge transfer from O to Mn x, y and z are respectively
(C) due to both d-d-transition and charge transfer (A) 1,2,3 (B) 1,5,3 (C) 1,3,5 (D) 5,3,1
(D) none of these
17. When KMnO4 solution is added to hot oxalic acid
7. During estimation of oxalic acid Vs KMnO4 , self solution, the decolourisation is slow in the beginning
indicator is but becomes instantaneous after some time. This is
(A) KMnO4 (B) oxalic acid because
(C) K 2 SO4 (D) MnSO4 (A) Mn2+ acts as auto catalyst
(B) CO2 is formed
8. A compound of mercury used in cosmetics, in
(C) Reaction is exothermic
Ayurvedic and Yunani medicines and known as
(D) MnO4− catalyses the reaction.
Vermilon is
(A) HgCl2 (B) HgS
18. The higher oxidation states of transition elements are
(C) Hg 2 Cl2 (D) HgI
found to be in the combination with A and B, which
KI dil 2 SO4 are
9. ↑ Y(g) ⟵ CuSO4 ⟶ X (Blue colour), X and Y are
(A) F, O (B) O, N (C) O, Cl (D) F, Cl
(A) X = I2 , Y = [Cu(H2 O)4 ]2+
(B) X = [Cu(H2 O)4 ]2+ , Y = I2

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19. Pick out the incorrect statement: (A) MnO2−4 is quite strongly oxidizing and stable only
(A) MnO2 dissolves in conc. HCl, but does not form in very strong alkalies. In dilute alkali,neutral
Mn4+ ions solutions, it disproportionates.
(B) MnO2 oxidizes hot concentrated H2 SO4 liberating (B) In acidic solutions, MnO4− is reduced to Mn2+ and
oxygen thus, KMnO4 is widely used as oxidising agent
(C) K 2 MnO4 is formed when MnO2 in fused KOH is (C) KMnO4 does not acts as oxidising agent in alkaline
oxidised by air, KNO3 , PbO2 or NaBiO3 medium
(D) Decomposition of acidic KMnO4 is not catalysed (D) KMnO4 is manufactured by the fusion of
by sunlight. pyrolusite ore with KOH in presence of air or KNO3 ,
20. 1 mole of Fe2+ ions are oxidised to Fe3+ ions with the followed by electrolytic oxidation in strongly alkaline
help of (in acidic medium) solution.
(A) 1/5 moles of KMnO4 31. The aqueous solution of CuCrO4 is green because it
(B) 5/3 moles of KMnO4 contains
(C) 2/5 moles of KMnO4 (A) green Cu2+ ions
(D) 5/2 moles of KMnO4 (B) green CrO4 2− ions
21. The metals present in insulin and haemoglobin are (C) blue Cu2+ ions and green CrO2− 4 ions

respectively (D) blue Cu2+ ions and yellow CrO4 2− ions

(A) Zn, Hg (B) Zn, Fe 32. Manganese steel is used for making railway tracks
(C) Co, Fe (D) Mg, Fe because
(A) it is hard with high percentage of Mn
22. The rusting of iron is formulated as Fe2 O3 ⋅ xH2 O (B) it is soft with high percentage of Mn
which involves the formation of (C) it is hard with small concentration of manganese
(A) Fe2 O3 (B) Fe(OH)3 with impurities
(C) Fe(OH)2 (D) Fe2 O3 + Fe(OH)3 (D) it is soft with small concentration of manganese
23. Metre scales are made-up of alloy with impurities
(A) invar (B) stainless steel 33. In nitroprusside ion, the iron exists as Fe2+ and NO as
(C) electron (D) magnalium NO+ rather than Fe3+ and NO respectively. These
24. A metal M which is not affected by strong acids like forms of ions are established with the help of
conc. HNO3 , conc. H2 SO4 and conc. solution of (A) Magnetic moment in solid state
alkalis like NaOH, KOH forms MCl3 which finds use for (B) thermal decomposition method
toning in photography. The metal M is (C) by reaction with KCN
(A) Ag (B) Hg (C) Au (D) Cu (D) by action with K 2 SO4
25. Solid CuSO4 ⋅ 5H2 O having covalent, ionic as well as 34. Transition elements in lower oxidation states act as
co-ordinate bonds. Copper atom/ion forms co- Lewis acid because
ordinate bonds with water. (A) they form complexes
(A) 1 (B) 2 (C) 3 (D) 4 (B) they are oxidising agents
(C) they donate electrons
26. KMnO4 + HCl ⟶ H2 O + X(g), X is a (acidified) (D) they do not show catalytic properties
(A) red liquid (B) violet gas
(C) greenish yellow gas (D) yellow-brown gas 35. The Ziegler-Natta catalyst used for polymerisation of
ethene and styrene is TiCl4 + (C2 H5 )3 Al, the
27. Purple of Cassius is:
catalysing species (active species) involved in the
(A) Pure gold
polymerisation is
(B) Colloidal solution of gold
(A) TiCl4 (B) TiCl3 (C) TiCl2 (D) TiCl
(C) Gold (I) hydroxide
(D) Gold (III) chloride 36. The electrons which take part in order to exhibit
variable oxidation states by transition metals are
28. Amongst the following species, maximum covalent
(A) ns only
character is exhibited by
(B) (n − 1)d only
(A) FeCl2 (B) ZnCl2 (C) HgCl2 (D) CdCl2
(C) ns and (n-1)d only but not np
29. Number of moles of SnCl2 required for the reduction (D) (n-1)d and np only but not ns
of 1 mole of K 2 Cr2 O7 into Cr2 O3 is
37. 'Bordeaux mixture' is used as a fungicide. It is a
(in acidic medium)
mixture of
(A) 3 (B) 2 (C) 1 (D) 1/3
(A) CaSO4 + Cu(OH)2 (B) CuSO4 + Ca(OH)2
30. Pick out the incorrect statement: (C) CuSO4 + CaO (D) CuO + CaO

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38. Which of the following reaction is possible at anode?

(A) 2Cr 3+ + 7H2 O ⟶ Cr2 O2−
7 + 14H
+

(B) F2 ⟶ 2 F −
1
(C) O2 + 2H + ⟶ H2 O
2
(D) None of these
39. Colourless solutions of the following four salts are
placed separately in four different test tubes and a
strip of copper is dipped in each one of these. Which
solution will turn blue?
(A) KNO3 (B) AgNO3
(C) Zn(NO3 )2 (D) ZnSO4
40. Peacock ore is:
(A) FeS2 (B) CuFeS2
(C) CuCO3 (D) Cu(OH)2
41. When acidified KMnO4 is added to hot oxalic acid
solution, the decolourization is slow in the beginning,
but becomes very rapid after some time. This is
because:
(A) Mn2+ acts as autocatalyst
(B) CO2 is formed as the product
(C) Reaction is exothermic
(D) MnO4− catalyses the reaction

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EXERCISE-II
10. An element of 3d-transition series shows two
1. Potash alum is a double salt, its aqueous solution
oxidation states x and y, differ by two units then
shows the characteristics of
(A) compounds in oxidation state x are ionic if x > y
(A) Al3+ ions
(B) compounds in oxidation state x are ionic if x < y
(B) K + ions
(C) compounds in oxidation state y are covalent if
(C) SO4 2− ions
x<y
(D) Al3+ ions but not K + ions
(D) compounds in oxidation state y are covalent if
2. Mercury is a liquid at 0∘ C because of y<x
(A) very high ionisation energy
11. To an acidified dichromate solution, a pinch of Na 2 O2
(B) weak metallic bonds
is added and shaken. What is observed:
(C) high heat of hydration
(A) blue colour
(D) high heat of sublimation
(B) Orange colour changing to green
3. The correct statement(s) about transition elements (C) Copious evolution of oxygen
is/are (D) Bluish - green precipitate
(A) the most stable oxidation state is +3 and its
12. Amongst CuF2 , CuCl2 and CuBr2
stability decreases across the period
(A) only CuF2 is ionic
(B) transition elements of 3 d-series have almost
(B) both CuCl2 and CuBr2 are covalent
same atomic sizes from Cr to Cu
(C) CuF2 and CuCl2 are ionic but CuBr2 is covalent
(C) the stability of +2 oxidation state increases across
(D) CuF2 , CuCl2 as well as CuBr2 are ionic
the period
(D) some transition elements like Ni, Fe, Cr may show 13. CuSO4 (aq) + 4NH3 ⟶ X, then X is
zero oxidation state in some of their compounds (A) [Cu(NH3 )4 ]2+
(B) paramagnetic
4. Which of the following statements concern with
(C) Coloured
transition metals?
(D) of a magnetic moment of 1.73BM
(A) compounds containing ions of transition elements
are usually coloured 14. Amphoteric oxide(s) of Mn is/are
(B) Zinc has lowest melting point among 3d-series (A) MnO2 (B) Mn3 O4
elements (C) Mn2 O7 (D) MnO
(C) they show variable oxidation states, which differ
15. Acidified KMnO4 can be decolourised by
by two units only
(A) SO2 (B) H2 O2
(D) they easily form complexes
(C) FeSO4 (D) Fe2 (SO4 )3
5. Correct statement(s) is/are
16. The lanthanide contraction is responsible for the fact
(A) an acidified solution of K 2 Cr2 O7 liberates iodine
that
from KI
(A) Zr and Hf have same atomic sizes
(B) K 2 Cr2 O7 is used as a standard solution for
(B) Zr and Hf have same properties
estimation of Fe2+ ions
(C) Zr and Hf have different atomic sizes
(C) in acidic medium, M = N/6 for K 2 Cr2 O7
(D) Zr and Hf have different properties
(D) (NH4 )2 Cr2 O7 on heating decomposes to yield
Cr2 O3 through an endothermic reaction 17. Ion(s) having non zero magnetic moment (spin only)
is/are
6. The highest oxidation state among transition
(A) Sc 3+ (B) Ti3+ (C) Cu2+ (D) Zn2+
elements is
(A) +7 by Mn (B) +8 by Os Question No. 18 to 27
(C) +8 by Ru (D) +7 by Fe Questions given below consist of two statements each
printed as Assertion (A) and Reason (R); while
7. Amphoteric oxide(s) is/are answering these questions you are required to choose
(A) Al2 O3 (B) SnO (C) ZnO (D) Fe2 O3 any one of the following four responses:
8. Interstitial compounds are formed by (A) if both (A) and (R) are true and (R) is the correct
(A) Co (B) Ni (C) Fe (D) Ca explanation of (A)
9. The catalytic activity of transition elements is related (B) if both (A) and (R) are true but (R) is not correct
to their explanation of (A)
(A) variable oxidation states (C) if (A) is true but (R) is false
(B) surface area (D) if (A) is false and (R) is true
(C) complex formation ability 18. Assertion: KMnO4 is purple in colour due to charge
(D) magnetic moment transfer.
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Reason: In MnO4− , there is no electron present in d-

orbitals of manganese.
19. Assertion: K 2 CrO4 has yellow colour due to charge
transfer.
Reason: CrO2− 4 ion is tetrahedral in shape.
20. Assertion: The highest oxidation state of chromium in
its compounds is +6 .
Reason: Chromium atom has only six electrons in ns
and (n − 1)d orbitals.
21. Assertion: CrO3 reacts with HCl to form chromyl
chloride gas.
Reason: Chromyl chloride (CrO2 Cl2 ) has tetrahedral
shape.
22. Assertion: Zinc does not show characteristic
properties of transition metals.
Reason: In zinc outermost shell is completely filled.
23. Assertion: Tungsten has a very high melting point.
Reason: Tungsten is a covalent compound.
24. Assertion: Equivalent mass of KMnO4 is equal to one-
third of its molecular mass when it acts as an
oxidising agent in an alkaline medium.
Reason: Oxidation number of Mn is +7 in KMnO4 .
25. Assertion: Ce4+ is used as an oxidising agent in
volumetric analysis.
Reason: Ce4+ has the tendency of attain +3 oxidation
state.
26. Assertion: Promethium is a man made element.
Reason: It is radioactive and has been prepared by
artificial means.
27. Assertion: Cu+ ion is colourless.
Reason: Four water molecules are coordinated to
Cu+ ion in water.

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EXERCISE-III [JEE MAIN PYQs]

9. The correct order of the first ionization enthalpies is:
1. Which series of reactions correctly represents
[JEE MAIN 2019]
chemical relations related to iron and its compound?
(A) Ti < Mn < Zn < Ni
[JEE MAIN 2014]
dill H2 SO4 H2 SO4 ,O2 heat
(B) Ti < Mn < Ni < Zn
(A) Fe ⟶ FeSO4 ⟶ Fe2 (SO4 )3 ⟶ Fe (C) Mn < Ti < Zn < Ni
O2 , heat dill 2 SO4 heat (D) Zn < Ni < Mn < Ti
(B) Fe ⟶ FeO ⟶ FeSO4 ⟶ Fe
Cl2 , heat heat,air Zn 10. Thermal decomposition of a Mn compound (X) at
(C) Fe ⟶ FeCl3 ⟶ FeCl2 ⟶ Fe
O2 ,heat CO,600∘ C CO,700∘ C 513K results in compound Y, MnO2 and a gaseous
(D) Fe ⟶ Fe3 O4 ⟶ FeO ⟶ Fe product MnO2 reacts with NaCl and concentrated
2. The equation which is balanced and represents the H2 SO4 to give pungent gas Z. X, Y, and Z,
correct product(s) is : [JEE MAIN 2014] respectively, are: [JEE MAIN 2019]
(A) Li2 O + 2KCl → 2LiCl + K 2 O (A) KMnO4 , K 2 MnO4 and Cl2
(B) K 2 MnO4 , KMnO4 and SO2
(B) [CoCl(NH3 )5 ]+ + 5H + → Co2+ + 5NH4+ + Cl−
excess, NaOH (C) K 3 MnO4 , K 2 MnO4 and Cl2
(C)[Mg(H2 O)6 ]2+ + ( EDTA )4− ⟶ (D) K 2 MnO4 , KMnO4 and Cl2
[Mg( EDTA )]2+ + 6H2 O
(D) CuSO4 + 4KCN → K 2 [Cu(CN)4 ] + K 2 SO4 11. Match the catalysts (Column-I) with products
(Column-II) [JEE MAIN 2019]
3. The colour of KMnO4 is due to : Column-1 Column-2
(A) M → L charge transfer transition (Catalyst) (Product)
(B) d − d transition [JEE MAIN 2015] (A) V2 O5 (i) Polyethylene
(C) L → M charge transfer transition (B) TiCl4 /Al(Me)3 (ii) ethanol
(D) σ − σ∗ transition (C) PdCl2 (iii) H2SO4
4. When XO2 is fused with an alkali metal hydroxide in (D) Iron Oxide (iv) NH3
presence of an oxidizing agent such as KNO3 ; a dark (A) (A)-(iii); (B)-(iv); (C)-(i); (D)-(ii)
green product is formed which disproportionates in (B) (A)-(ii);(B)-(iii); (C)-(i); (D)-(iv)
acidic solution to afford a dark purple solution. X is : (C) (A)-(iii); (B)-(i); (C)-(ii); (D)-(iv)
[JEE MAIN 2018] (D) (A)-(iv); (B)-(iii); (C)-(ii); (D)-(i)
(A) Ti (B) V (C) Cr (D) Mn 12. The incorrect statement is: [JEE MAIN 2020]
5. The transition element that has lowest enthalpy of (A) Manganate and permanganate ions are
atomisation is : [JEE MAIN 2019] Tetrahedral
(A) Zn (B) Cu (C) Fe (D) V (B) In manganate and permanganate ions, the π-
bonding takes place by overlap of p-orbitals of oxygen
6. Consider the following reduction processes : and d orbitals of manganese
[JEE MAIN 2019] (C) Manganate and permanganate ions are
Zn2+ + 2e− → Zn(s); E o = −0.76 V paramagnetic
Ca2+ + 2e− → Ca(s); E o = −2.87 V (D) Manganate ion is green in colour and
Mg 2+ + 2e− → Mg(s); E o = −2.36 V permanganate ion is purple in colour
Ni2+ + 2e− → Ni(s); E o = −0.25 V
The reducing power of the metals increases in the 13. The third ionization enthalpy is minimum for:
order : [JEE MAIN 2020]
(A) Ca < Mg < Zn < Ni (A) Co (B) Fe (C) Ni (D) Mn
(B) Zn < Mg < Ni < Ca 14 The atomic radius of Ag is closest to:
(C) Ni < Zn < Mg < Ca [JEE MAIN 2020]
(D) Ca < Zn < Mg < Ni (A) Au (B) Ni (C) Cu (D) Hg
7. The electrolytes usually used in the electroplating of 15. Identify the element for which electronic
gold and silver, respectively, are : configuration in +3 oxidation state is [Ar]3d5 :
[JEE MAIN 2019] [JEE MAIN 2021]
(A) [Au(CN2 )]− and [Ag(CN)2 ]− (A) Ru (B) Mn (C) Co (D) Fe
(B) [Au(NH3 )2 ]+ and [Ag(CN)2 ]−
(C) [Au(CN2 )]− and [Ag(Cl)2 ]− 16. Potassium permanganate on heating at 513 K gives a
(D) [Au(OH)4 ]− and [Ag(OH)2 ]− product which is: [JEE MAIN 2021]
(A) paramagnetic and colourless
8. The element that usually does NOT show variable (B) diamagnetic and green
oxidation states is: [JEE MAIN 2019] (C) diamagnetic and colourless
(A) Cu (B) Sc (C) V (D) Ti (D) paramagnetic and green
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17. In the ground state of atomic Fe(Z = 26), the spin-only Assertion (A) : In aqueous solutions Cr 2+ is reducing
magnetic moment is _______ × 10−1 BM. (Round off to while Mn3+ is oxidising in nature.
the nearest integer). Reason (R) : Extra stability to half filled electronic
[Given : √3 = 1.73, √2 = 1.41] [JEE MAIN 2021] configuration is observed than incompletely filled
electronic configuration.
18. The reaction of zinc with excess of aqueous alkali, In the light of the above statement, choose the most
evolves hydrogen gas and gives appropriate answer from the options given below:
[JEE MAIN 2022] (A) Both (A) and (R) are true and (R) is the correct
(A) Zn(OH)2 (B) ZnO explanation of (A)
(C) [Zn(OH)4 ]2− (D) [ZnO2 ]2− (B) Both (A) and (R) are true but (R) is not the correct
19. The total number of Mn = O bonds in Mn2 O7 is explanation of (A)
[JEE MAIN 2022] (C) (A) is false but (R) is true
(A) 4 (B) 5 (C) 6 (D) 3 (D) (A) is true but (R) is false
20. Dihydrogen reacts with CuO to give 29. Which of the following compounds show colour due to
[JEE MAIN 2022] d-d transition? [JEE MAIN 2024]
(A) CuH2 (B) Cu (A) CuSO4 . 5H2 O (B) K 2 Cr2 O7
(C) Cu2 O (D) Cu(OH)2 (C) K 2 CrO4 (D) KMnO4
21. Among the following, which is the strongest oxidizing 30. NaCl reacts with conc. H2 SO4 and K 2 Cr2 O7 to give
agent? [JEE MAIN 2022] reddish fumes (B), which react with NaOH to give
(A) Mn3+ (B) Fe3+ (C) Ti3+ (D) Cr 3+ yellow solution (C). (B) and (C) respectively are ;
[JEE MAIN 2024]
22. The disproportionation of MnO2− 4 in acidic medium (A) CrO2 Cl2 , Na 2 CrO4
resulted in the formation of two manganese (B) Na 2 CrO4 , CrO2 Cl2
compounds A and B. If the oxidation state of Mn in B is (C) CrO2 Cl2 , KHSO4
smaller than that of A, then the spin-only magnetic (D) CrO2 Cl2 , Na 2 Cr2 O7
moment (μ) value of B in BM is ________ . (Nearest
integer) [JEE MAIN 2022] 31. Choose the correct option having all the elements with
d10 electronic configuration from the following:
23. The spin-only magnetic moment value of the (A) 27 Co, 28 Ni, 26 Fe, 24 Cr [JEE MAIN 2024]
compound with strongest oxidizing ability among (B) 29 Cu, 30 Zn, 48 Cd, 47 Ag
MnF4 , MnF3 and MnF2 is ________ B.M. [nearest integer] (C) 46 Pd, 28 Ni, 26 Fe, 24 Cr
[JEE MAIN 2022] (D) 28 Ni, 24 Cr, 26 Fe, 29 Cu
24. The spin-only magnetic moment value of M 3+ ion (in 32. In chromyl chloride test for confirmation of Cl− ion, a
gaseous state) from the pairs Cr 3+ /Cr 2+ , Mn3+ /Mn2 , yellow solution is obtained. Acidification of the
Fe3+ /Fe2+ and Co3+ /Co2+ that has negative standard solution and addition of amyl alcohol and 10% H2 O2
electrode potential is _________ B.M. [Nearest integer] turns organic layer blue indicating formation of
[JEE MAIN 2022] chromium pentoxide. The oxidation state of chromium
25. The number of statement(s) correct from the in that is [JEE MAIN 2024]
following for copper (at no. 29) is/are ________ . (A) +6 (B) +5 (C) +10 (D) +3
[JEE MAIN 2022] 33. In alkaline medium. MnO4− oxidises I − to
(A) Cu (II) complexes are always paramagnetic [JEE MAIN 2024]
(B) Cu (I) complexes are generally colourless (A) IO− (B) IO− (C) I2 (D) IO−
4 3
(C) Cu(I) is easily oxidized
(D) In Fehling solution, the active reagent has Cu (I) 34. Which of the following statements are correct about
Zn, Cd and Hg ? [JEE MAIN 2024]
26. Acidified potassium permanganate solution oxidises A. They exhibit high enthalpy of atomization as the d-
oxalic acid. The spin-only magnetic moment of the subshell is full.
manganese product formed from the above reaction is B. Zn and Cd do not show variable oxidation state
________ . B.M. (Nearest Integer) [JEE MAIN 2022] while Hg shows +I and + II.
27. The transition metal having highest 3rd ionisation C. Compounds of Zn, Cd and Hg are paramagnetic in
enthalpy is: [JEE MAIN 2024] nature.
(A) Cr (B) Mn (C) V (D) Fe D. Zn, Cd and Hg are called soft metals.
Choose the most appropriate from the options given
28. Given below are two statements : one is labelled as below:
Assertion (A) and the other is labelled as Reason (R). (A) B, D only (B) B, C only
[JEE MAIN 2024] (C) A, D only (D) C, D only
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35. Match List-I with List-II [JEE MAIN 2024] C. CrO is a basic oxide
List-I List-II D. V2 O5 does not react with acid
Species Electronic distribution Choose the correct answer from the options given
(A) Cr +2 (I) 3d8 below:
(B) Mn +
(II) 3d3 4s1 (A) A, B and D only (B) A and C only
(C) Ni +2
(III) 3d4 (C) A, B and C only (D) B and C only
(D) V +
(IV) 3d5 4s1
41. The 'Spin only' Magnetic moment for [Ni(NH3 )6 ]2+ is
Choose the correct answer from the options given
____ × 10−1 BM. [JEE MAIN 2024]
below:
(given = Atomic number of Ni: 28)
(A) (A)-I, (B)-II, (C)-III, (D)-IV
(B) (A)-III, (B) - IV, (C) - I, (D)-II 42. Number of moles of H + ions required by 1 mole of
(C) (A)-IV, (B)-III, (C)-I, (D)-II MnO4− to oxidise oxalate ion to CO2 is ____.
(D) (A)-II, (B)-I, (C)-IV, (D)-III [JEE MAIN 2024]
36. The orange colour of K 2 Cr2 O7 and purple colour of 43. In the reaction of potassium dichromate, potassium
KMnO4 is due to [JEE MAIN 2024] chloride and sulfuric acid (conc.), the oxidation state
(A) Charge transfer transition in both. of the chromium in the product is (+) ______.
(B) d → d transition in KMnO4 and charge transfer [JEE MAIN 2024]
transitions in K 2 Cr2 O7 .
44. The correct decreasing order of spin only magnetic
(C) d → d transition in K 2 Cr2 O7 and charge transfer
moment values (BM) of Cu+ , Cu2+ , Cr 2+ and Cr 3+ ions
transitions in KMnO4 .
is : [JEE MAIN 2025]
(D) d → d transition in both.
(A) Cr 3+ > Cr 2+ > Cu+ > Cu2+
37. Alkaline oxidative fusion of MnO2 gives "A" which on (B) Cu+ > Cu2+ > Cr 3+ > Cr 2+
electrolytic oxidation in alkaline solution produces B. (C) Cr 2+ > Cr 3+ > Cu2+ > Cu+
A and B respectively are: [JEE MAIN 2024] (D) Cu2+ > Cu+ > Cr 2+ > Cr 3+
(A) Mn2 O7 and MnO4−
45. The first transition series metal ' M ' has the highest
(B) MnO4 2− and MnO4−
enthalpy of atomisation in its series. One of its aquated
(C) Mn2 O3 and MnO4 2−
ion ( M n+ ) exists in green colour. The nature of the
(D) MnO4 2− and Mn2 O7
oxide formed by the above M n+ ion is:
38. A and B formed in the following reactions are: [JEE MAIN 2025]
[JEE MAIN 2024] (A) basic (B) neutral
CrO2 Cl2 + 4NaOH → A + 2NaCl + 2H2 O (C) amphoteric (D) acidic
A + 2HCl + 2H2 O2 → B + 3H2 O
46. Pair of transition metal ions having the same number
(A) A = Na2 CrO4 , B = CrO5
of unpaired electrons is [JEE MAIN 2025]
(B) A = Na2 Cr2 O4 , B = CrO4
(A) Ti3+ , Mn2+ (B) Ti2+ , Co2+
(C) A = Na2 Cr2 O7 , B = CrO3
(C) Fe3+ , Cr 2+ (D) V 2+ , Co2+
(D) A = Na2 Cr2 O7 , B = CrO5
47. Given below are two statements: [JEE MAIN 2025]
39. Identify correct statements from below:
Statement I : CrO3 is a stronger oxidizing agent than
[JEE MAIN 2024]
MoO3
A. The chromate ion is square planar.
Statement II : Cr(VI) is more stable than Mo(VI)
B. Dichromates are generally prepared from
In the light of the above statements, choose the correct
chromates.
answer from the options given below
C. The green manganate ion is diamagnetic.
A Statement I is true but Statement II is false
D. Dark green coloured K 2 MnO4 disproportionates in
B Both Statement I and Statement II are true
a neutral or acidic medium to give permanganate.
C Both Statement I and Statement II are false
E. With increasing oxidation number of transition
(D) Statement I is false but Statement II is true
metal, ionic character of the oxides decreases.
Choose the correct answer from the options given 48. The metal ions that have the calculated spin-only
below: magnetic moment value of 4.9 B.M. are :
(A) B, C, D only (B) A, D, E only [JEE MAIN 2025]
(C) A, B, C only (D) B, D, E only (A) Cr 2+ (B) Fe2+ (C) Fe3+ (D) Co2+
(E) Mn 3+
40. Choose the correct statements from the following
Choose the correct answer from the options given
[JEE MAIN 2024]
below:
A. Mn2 O7 is an oil at room temperature
(A) A, D and E Only (B) A, B and E Only
B. V2 O4 reacts with acid to give VO2+
2
(C) A, C and E Only (D) B and E Only
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49. The correct option with order of melting points of the (C) UK silver coin (III) Cu, Zn
pairs (Mn, Fe ), (Tc, Ru ) and ( Re, Os ) is :
[JEE MAIN 2025] (D) Stainless steel (IV) Cu, Sn
(A) Fe < Mn, Ru < Tc and Re < Os
Choose the correct answer from the options given
(B) Fe < Mn, Ru < Tc and Os < Re
below : [JEE MAIN 2025]
(C) Mn < Fe, Tc < Ru and Re < Os
(A) (A)-(IV), (B)-(II), (C)-(III), (D)-(I)
(D) Mn < Fe, Tc < Ru and Os < Re
(A) (A)-(IV), (B)-(III), (C)-(I), (D)-(II)
50. The amphoteric oxide among V2 O3 , V2 O4 and V2 O5 , (C) (A)-(III), (B)-(I), (C)-(IV), (D)-(II)
upon reaction with alkali leads to formation of an (D) (A)-(III), (B)-(IV), (C)-(II), (D)-(I)
oxide anion. The oxidation state of V in the oxide anion
56. Consider the following reactions
is : [JEE MAIN 2025]
[JEE MAIN 2025]
(A) +4 (B) +5 (C) +3 (D) +7 KOH H2 SO4
K 2 Cr2 O7 → [ A] → [ B] + K 2 SO4
51. The metal ion whose electronic configuration is not −H2 O −H2 O
affected by the nature of the ligand and which gives a The products [A] and [B], respectively are :
violet colour in non-luminous flame under hot (A) K 2 Cr(OH)6 and Cr2 O3
condition in borax bead test is [JEE MAIN 2025] (B) K 2 CrO4 and Cr2 O3
(A) Cr 3+ (B) Ti3+ (C) Ni2+ (D) Mn2+ (C) K 2 CrO4 and K 2 Cr2 O7
(D) K 2 CrO4 and CrO
52. Match List - I with List - II. [JEE MAIN 2025]
57. The correct set of ions (aqueous solution) with same
List - II
colour from the following is: [JEE MAIN 2025]
List - I (Spin only
(A) V 2+ , Cr 3+ , Mn3+
(Transition magnetic
(B) Ti4+ , V 4+ , Mn2+
metal ion) moment
(C) Sc 3+ , Ti3+ , Cr 2+
(B.M.))
(D) Zn2+ , V 3+ , Fe3+
(A) Ti3+ (I) 3.87 58. Among, Sc, Mn, Co and Cu , identify the element with
highest enthalpy of atomisation. The spin only
(B) V 2+ (II) 0.00
magnetic moment value of that element in its +2
(C) Ni2+ (III) 1.73 oxidation state is ____ BM (in nearest integer).
[JEE MAIN 2025]
(D) Sc 3+ (IV) 2.84
59. Consider the following reactions [JEE MAIN 2025]
Choose the correct answer from the options given A + NaCl + H2 SO4 → CrO2 Cl2 + Side Products
Little
below : amount
(A) (A) - (III), (B) - (I), (C) - (IV), (D) - (II) CrO2 Cl2 (Vapour) + NaOH → B + NaCl + H2 O
(B) (A) - (II), (B) - (IV), (C) - (I), (D) - (III) B + H + → C + H2 O
(C) (A) - (III), (B) - (I), (C) - (II), (D) - (IV) The number of terminal ' O ' present in the compound
(D) (A) - (IV), (B) - (II), (C) - (III), (D) - (I) ' C ' is ____
53. Preparation of potassium permanganate from MnO2 60. The molar mass of the water insoluble product formed
involves two step process in which the 1 st step is a from the fusion of chromite ore (FeCr2 O4 ) with
reaction with KOH and KNO3 to produce Na 2 CO3 in presence of O2 is ____ gmol−1 .
(A) K 3 MnO4 (B) K 4 [Mn(OH)6 ] [JEE MAIN 2025]
(C) K 2 MnO4 (D) KMnO4 [JEE MAIN 2025]
61. Niobium (Nb) and ruthenium (Ru) have " x " and " y "
54. Which of the following ions is the strongest oxidizing number of electrons in their respective 4 d orbitals.
agent? (Atomic Number of Ce = 58, Eu = 63, Tb = The value of x + y is ____ . [JEE MAIN 2025]
65, Lu = 71 ) [JEE MAIN 2025]
(A) Lu3+ (B) Eu2+ (C) Tb4+ (D) Ce3+
55. Match List - I with List - II
List - I List - II

(A) Bronze (I) Cu, Ni

Fe, Cr,
(B) Brass (II)
Ni, C

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EXERCISE-IV [JEE Advanced PYQs] 10. [IIT-JEE 2005]

1. Amongst the following identify the species with an
atom in +6 oxidation state. [IIT-JEE 2000]
(A) MnO− 4
(B) Cr(CN)3−
6
(C) NiF62−
(D) CrO2 Cl2
2. Write the balanced chemical equations for developing
photographic films. [IIT-JEE 2000]
3. In the standardization of Na 2 S2 O3 using K 2 Cr2 O7 by
iodometry, the equivalent weight of K 2 Cr2 O7 is : Identify (A), (B) and (C). Also explain colour
[IIT-JEE 2001] difference between MCl4 and (B).
(A) (molecular weight )/2, ( molar mass )/2
11. Match the reactions in Column I with nature of the
(B) (molecular weight) /6
reactions/type of the products in Column II.
(C) (molecular weight )/3
[IIT-JEE 2007]
(D) same as molecular weight
Column I Column II
4. Anhydrous ferric chloride is prepared by : (A) O−
2 → O2 + O2
2−
(P) Redox reaction
[IIT-JEE 2002] (B) CrO4 + H →
2− +
(Q)One of the products
(A) heating hydrated ferric chloride at a high has trigonal planar
temperature in a stream of air. structure
(B) heating metallic iron in a stream of dry chlorine. (C) MnO− −
4 + NO2 + H →
+
(R) Dimeric bridged
(C) reaction of metallic iron with hydrochloric acid. tetrahedral metal
(D) reaction of metallic iron with nitric acid. ion
(D) NO3− + H2 SO4 + Fe2+ → (S) Disproportionation
5. When MnO2 is fused with KOH, a coloured compound
is formed. The product and its colour is: 12. Among the following, the coloured compound is :
[IIT-JEE 2003] [IIT-JEE 2008]
(A) K 2 MnO4 , green (A) CuCl (B) K 3 [Cu(CN)4 ]
(B) Mn2 O3 , brown (C) CuF2 (D) [Cu(CH3 CN)4 ]BF4
(C) Mn2 O4 , black
13. The oxidation number of Mn in the product of alkaline
(D) KMnO4 , purple
oxidative fusion of MnO2 is. [IIT-JEE 2009]
6. The product of oxidation of I − with MnO4− in alkaline
14. Reduction of the metal centre in aqueous
medium is: [IIT-JEE 2004]
permanganate ion involves: [IIT-JEE 2011]
(A) IO−
3 (B) I2 (C) IO− (D) IO−
4
(A) 3 electrons in neutral medium
7. The pair of compounds having metals in their highest (B) 5 electrons in neutral medium
oxidation state is: [IIT-JEE 2004] (C) 3 electrons in alkaline medium
(A) MnO2 , FeCl3 (D) 5 electrons in acidic medium
(B) [MnO4 ]− , CrO2 Cl2
15. The colour of light absorbed by an aqueous solution of
(C) [Fe(CN)6 ]2− , [Co(CN)6 ]3−
CuSO4 is: [IIT-JEE 2012]
(D) [NiCl4 ]2− , [Ni(CO)4 ].
(A) organge-red (B) blue-green
8. Which of the following pair of compounds is expected (C) yellow (D) violet
to exhibit same colour in aqueous solution?
16. Which of the following halides react(s) with AgNO3
[IIT-JEE 2005]
(aq) to give a precipitate that dissolves in
(A) FeCl3 , CuCl2
Na 2 S2 O3 (aq) ? [IIT-JEE 2012]
(B) VOCl2 , CuCl2
(A) HCl (B) HF (C) HBr (D) HI
(C) VOCl2 , FeCl2
(D) FeCl2 , MnCl2 17. Consider the following list of reagents:
[IIT-JEE 2012]
9. Give equations and describe the process for the
Acidified K 2 Cr2 O7 , alkaline
developing of black and white photographic film.
KMnO4 , CuSO4 , H2 O2 , Cl2 , O3 , FeCl3 , HNO3 and
When sodium thiosulphate solution is treated with
Na 2 S2 O3 . The total number of reagents that can
acidic solution turns milky white. Give the half
oxidise aqueous iodide to iodine is
reaction of the above described process.
[IIT-JEE 2005]

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18. The correct statement(s) about Cr 2+ and Mn3+ is

(are): [JEE Advanced 2015]
[Atomic numbers of Cr = 24 and Mn = 25 ]
(A) Cr 2+ is a reducing agent
(B) Mn3+ is an oxidizing agent
(C) Both Cr 2+ and Mn3+ exhibit d4 electronic
configuration
(D) When Cr 2+ is used as a reducing agent, the
chromium ion attains d5 electronic configuration.
19. Fe3+ is reduced to Fe2+ by using
[JEE Advanced 2015]
(A) H2 O2 in presence of NaOH
(B) Na 2 O2 in water
(C) H2 O2 in presence of H2 SO4
(D) Na 2 O2 in presence of H2 SO4
20. Fusion of MnO2 with KOH in presence of O2 produces
a salt W. Alkaline solution of W upon electrolytic
oxidation yields another salt X. The manganese
containing ion's present in W and X, respectively, are
Y and Z. Correct statement(s) is(are)
[JEE Advanced 2019]
(A) Y is diamagnetic in nature while Z is paramagnetic
(B) In aqueous acidic solution, Y undergoes
disproportionation reaction to give Z and MnO2
(C) Both Y and Z are coloured and have tetrahedral
shape
(D) In both Y and Z, π-bonding occurs between p-
orbitals of oxygen and d-orbitals of manganese
21. An acidified solution of potassium chromate was
layered with an equal volume of amyl alcohol. When
it was shaken after the addition of 1 mL of 3%H2 O2 , a
blue alcohol layer was obtained. The blue color is
due to the formation of a chromium (VI) compound '
X '. What is the number of oxygen atoms bonded to
chromium through only single bonds in a molecule of
X? [JEE Advanced 2020]

22. H2 S (5 moles) reacts completely with acidified

aqueous potassium permanganate solution. In this
reaction, the number of moles of water produced is 𝑥,
and the number of moles of electrons involved is 𝑦.
The value of (𝑥 + 𝑦) is ____.
[JEE Advanced 2023]

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ANSWER KEY
EXERCISE-I
1. B 2. A 3. B 4. B 5. A 6. B 7. A 8. B 9. B
10. A 11. B 12. D 13. B 14. C 15. A 16. B 17. A 18. A
19. D 20. A 21. B 22. D 23. A 24. C 25. D 26. C 27. B
28. C 29. A 30. C 31. D 32. A 33. A 34. A 35. B 36. C
37. B 38. A 39. B 40. D 41. A
EXERCISE-II
1. A,B,C 2. A,B 3. A,B,C,D 4. A,B, D 5. A,B,C 6. B,C 7. A,B,C 8. A,B,C
9. A,B,C 10. B,C 11. A,C 12. A,B 13. A,B,C,D 14. A,B 15. A,B,C 16. A,B
17. B,C 18. B 19. B 20. A 21. B 22. C 23. C 24. B
25. A 26. A 27. C
EXERCISE-III [JEE MAIN PYQs]
1. (D) 2. (B) 3. (C) 4. (D) 5. (A) 6. (C) 7. (A) 8. (B) 9. (B)
10. (A) 11. (C) 12. (C) 13. (B) 14. (A) 15. (D) 16. (D) 17. (49) 18. (C)
19. (C) 20. (B) 21. (A) 22. (4) 23. (5) 24. (4) 25. (3) 26. (6) 27. (B)
28. (A) 29. (A) 30. (A) 31. (B) 32. (A) 33. (D) 34. (A) 35. (B) 36. (A)
37. (B) 38. (A) 39. (D) 40. (B) 41. (28) 42. (8) 43. (6) 44. (C) 45. (A)
46. (D) 47. (A) 48. (B) 49. (D) 50. (B) 51. (C) 52. (A) 53. (C) 54. (C)
55. (B) 56. (C) 57. (A) 58. (4) 59. (6) 60. (160) 61. (11)
EXERCISE-IV [JEE Advanced PYQs]
1. (D)
2. C6 H4 (OH)2 + 2AgBr ⟶ 2Ag + C6 H4 O2 + 2HBr.
AgBr + 2Na 2 S2 O3 ⟶ Na 3 [Ag(S2 O3 )2 ] + NaBr
3. (B) 4. (B) 5. (A) 6. (A) 7. (B) 8. (B)
9. Developer is usually a weak reducing agent like potassium ferrous oxalate, an alkaline solution of pyrogallol or an alkaline
solution of quinol.
In the process of development of the photographic film, the exposed/activated AgBr grains are preferentially reduced by
one of the reducing agent described above.

The photographic film is then fixed by washing with hypo solution to remove the unreduced AgBr grains from the film.
AgBr + 2Na 2 S2 O3 ⟶ Na 3 [Ag(S2 O3 )2 ] + NaBr
S2 O3 2− + H2 O ⟶ 2SO2 + 2H + + 4e−
S2 O3 2− + 6H + ⟶ 2 S ↓ ( white milky) + 3H2 O
10. (A) is TiCl4 as it has no unpaired electron and is liquid at room temperature on account of covalent character because of
high polarising power of Ti+4 being covalent gets hydrolysed forming TiO2 (H2 O)2 and HCl(B) which fumes in air.
In [Ti(H2 O)6 ]Cl3 complex Ti(III) has one unpaired electron (3 d1 ) which gives violet/purple colour to d-d transition.

11. (A) − P, S; (B) − R; (C) − P, Q; (D) − (P). 12. (C) 13. 6 14. (A, C, D)/(A, D) 15. (A)
16. (A, C, D) 17. 7 18. (A, B, C) 19. (C, D) 20. (2,3,4)
21. 4
Blue colour compound of ' Cr ' is CrO5 .

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Oxygen atoms bonded to chromium through only single bonds = 4

22. 18

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