(Organic Chemistry) d-BLOCK ELEMENTS

TRANSITION ELEMENTS
Definition: They one often called 'transition elements' because their position in the periodic table is
between s-block and p-block elements Typically, the transition elements have an incompletely filled d-
level, are not considered as transition elements but they are d-block elements. Since Zn group has d10
configuration in their ground state as well as in stable oxidation state, they are not considered as
transition elements but they are d-block elements.
1st SERIES
Sc Ti V Cr Mn Fe Co Ni Cu
Z 21 22 23 24 25 26 27 28 29
4s 2 2 2 1 2 2 2 2 1
3d 1 2 3 5 5 6 7 8 10

2nd SERIES
Y Zr Nb Mo Tc Ru Rh Pd Ag
Z 39 40 41 42 43 44 45 46 47
5s 2 2 1 1 1 1 1 0 1
4d 1 2 4 5 6 7 8 10 10

3rd SERIES
La Hf Ta W Re Os Ir Pt Au
Z 57 72 73 74 75 76 77 78 79
6s 2 2 2 2 2 2 2 1 1
5d 1 2 3 4 5 6 7 9 10

4th SERIES
Ac Rf Db Sg Bh Hs Mt Ds Rg
Z 89 104 105 106 107 108 109 110 111
7s 2 2 2 2 2 2 2 2 1
5d 1 2 3 4 5 6 7 8 10
General Characteristics:
(i) Metallic character: They are all metal and good conductor of heat & electricity
(ii) Electronic configuration: (n − 1)d1−10 ns1−2

(iii) M.P.

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(Organic Chemistry) d-BLOCK ELEMENTS
(iv) Variation in atomic radius:

(v) Ionisation energy:

1st , 2nd , 3rd , IE, s are increasing from left to right for 1st Transition series, but not regularly.
For 2nd IECr > Fe > Mn and Cu > Zn
For 3rd IEMn > Cr > Fe and Z has highest.
Element Sc Ti V Cr Mn Fe Co Ni Cu
Atomic number 21 22 23 24 25 26 27 28
Electronic
M 3d1 4s 2 3 d2 4 s2 3 d3 4 s2 3d5 4s2 3 d5 4 s2 3d6 4s2 3d7 4s2 3 d10 4 s 2
configuration
M + 3 d1 4 s1 3 d2 4 s1 3d3 4s1 3 d5 3d5 4s1 3d6 4s1 3 d7 4 s1 3 d8 4 s1
M 2+ 3 d1 3 d2 3 d3 3 d1 3 d5 3 d6 3 d7 3 d8
M 3+ [Ar] 3 d1 3 d2 3 d3 3 d1 3 d5 3 d6 3 d7
Enthalpy of
atomization 326 473 515 397 281 416 425 430
Θ −1
Δ1 H /kJmol
Ionisation
Enthalpy,
I 631 656 650 653 717 762 758 736
Δ1 H Θ /kJ
mol−1
Δ1 H Θ II 1235 1309 1414 1592 1509 1561 1644 1752
III 2393 2657 2833 2990 3260 2962 3243 3402
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 .
(2) The lesser number of oxidation states at the extreme ends stems from either too few
electrons to lose or share (Sc, Ti) or too many d electrons (hence fewer orbitals
available in which to share electrons with others) for higher valence ( Cu, Zn).
(3) Thus, early in the series scandium(II) is virtually unknown and titanium (IV) is more
stable than Ti(III) or Ti(II).
(4) At the other end, the only oxidation state of zinc is +2 (no 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 O− 4 )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 .

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(Organic Chemistry) d-BLOCK ELEMENTS
(7) This is in contrast with the variability of oxidation states of non transition elements
where oxidation states normally differ by a unit of two.
(8) An interesting feature in the variability of oxidation states of the d-block elements is
noticed among the groups (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 are not.
(10) Low oxidation states are found when a complex compound has ligands capable of π-
acceptor character in 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 these
higher oxides, the acidic character is predominant. Thus, Mn2 O7 gives HMnO4 and CrO3
gives H2 CrO4 and H2 Cr2 O7 . V2 O5 is, however, amphoteric though mainly acidic and it
gives VO3−4 as well as VO
2+
salts. In vanadium there is gradual change from the basic
V2 O3 to less basic V2 O4 and to amphoteric V2 O5 . V2 O4 dissolves in acids to give VO2+
salts. Similarly, V2 O5 reacts with alkalies as well as acids to give VO3−
4 and
VO4 respectively. The well characterised CrO is basic but Cr2 O3 is amphoteric.
+

Oxidation state of the 𝐈st transition series Most common ones are in bole types:
𝐒𝐜 𝐓𝐢 𝐕 𝐂𝐫 𝐌𝐧 𝐅𝐞 𝐂𝐨 𝐍𝐢 𝐂𝐮 𝐙𝐧
+1 +1
+2 +2 +2 +2 +2 +2 +2 +2 +2
+3 +3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7
Trends in stability of higher oxidation state:
(1) Table shows the stable halides of the 3 d series of transition metals. The highest oxidation
numbers are achieved in TiX4 (tetrahalides), VF5 and CrF6 . The +7 state for Mn is not
represented in simple halides but MnO3 F is known, and beyond Mn no metal has a trihalide
except FeX 3 and CoF3 .
(2) The ability of fluorine to stabilise the highest oxidation state is due to either higher lattice
energy as in the case of CoF3 , or higher bond enthalpy terms for the higher covalent
compounds, e.g., VF5 and CrF6 .
(3) Although V V is represented only by VF5 , the other halides, however, undergo hydrolysis to
give oxohalides, VOX3 .

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(4) Another feature of fluorides is their instability in the low oxidation states
e.g., VX2 (X = CI, Br or I)
Formulas of halides of 𝟑𝐝-metals
Oxidation Number
+6 CrF6
+5 VF5 CrF5
+4 TiX4 VX4I CrF4 MnF4
+3 TiX3 III VX3 CrF3 MnF3 FeX 3I CoF3 CuX2II ZnX 2
+2 TiX2 VX2 CrF2 MnX 2 FeX 2 CoX NiX 2 CuX III
+1

Key : X = F → I; X I = F → Br; X II = F → Cl; X III = Cl → I

and the same applies to CuX. On the other hand, all Cu(II) halides are known except the iodide.
In this case, Cu2+ oxidises I − to I2 :
2Cu2+ + 4I − → Cu2 I2 ( s) + I2
(5) However, many copper (I) compounds are unstable in aqueous solution and undergo
disproportionation.
2Cu+ → Cu2+ + Cu
(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 .
(9) Beyond Group 7, no higher oxides of Fe above Fe2 O3 , are 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 VO2+ , V IV as VO2+ and TiIV as TiO2+
(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
COLOURED ION:
Colour: (aquated)
Ta4+ ⟶ colourless Sc 3+ ⟶ colourless
V 4+ ⟶ blue Ti3+ ⟶ purple
V ⟶ violet
2+
V 3+ ⟶ green
Cr 3+ ⟶ green Cr 2+ ⟶ blue
Mn ⟶ light pink
2+
Mn3+ ⟶ violet
Fe3+ ⟶ yellow Fe2+ ⟶ light green
Ni2+ ⟶ green Co2+ ⟶ pink
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(Organic Chemistry) d-BLOCK ELEMENTS
Zn2+ ⟶ colourless Cu2+ ⟶ blue
CATALYTIC PROPERTIES
(1) The transition metals and their compounds are known for their catalytic activity. This
activity is ascribed to their ability to adopt multiple oxidation states and to form complexes.
Vanadium (V) oxide (in Contact Process), finely divided iron (in Haber's Process), and nickel (in
Catalytic 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).
(4) Also because the transition metal ions can change their oxidation states, they become more
effective as catalysts. For example, iron(III) catalyses the reaction between iodide and
persulphateions.
2I − + S2 O8 2− → I2 + 2SO4 2−
An explanation of this catalytic action can be given as:
2Fe3+ + 2I − → 2Fe2+ + I2
2Fe2+ + S2 O2−8 → 2Fe
3+
+ 2SO4 2−
Catalyst Used
TiCl3 ⟶ Used as the Ziegler-Natta catalyst in the production of polythene.
V2 O5 ⟶ Convert SO2 to SO3 in the contact process for making H2 SO4
MnO2 ⟶ Used as a catalyst to decompose KClO3 to give O2
Fe ⟶ Promoted iron is used in the Haber-Bosch process for making NH3
FeCl3 ⟶ Used in the production of CCl4 from CS2 and Cl2
PdCl2 ⟶ Wacker process for converting C2 H4 + H2 O + PdCl2 to CH3 CHO + 2HCl + Pd.
Pd ⟶ Used for hydrogenation (e.g. phenol to cyclohexanone).
Pt/PtO ⟶ Adams catalyst, used for reductions.
Pt ⟶ Formerly used for SO2 ⟶ SO3 in in the contace process for making H2 SO4
Pt/Rh ⟶ Formerly used in the ostwald process for making HNO3 to oxidize NH3 to NO
Is used in the direct process for manufacture of (CH3 )2 SiCl2 used to make silicones.
Cu ⟶

Oxidation of cyclohexanol/cyclohexanone mixture to adipic acid which is used

Cu/V ⟶
to make nylone- 66
CuCl2 ⟶ Decon process of making Cl2 from HCl
Raney nickel, numerous reduction processes (e.g. manufacture of
Ni ⟶ hexamethylenediamine, productiomn of H2 from NH3 , reducing anthraquinone
to anthraquinol in the production of H2 O2

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Formation of Interstitial Compounds
Interstitial compounds are those which are formed when small atoms like H, C or N are trapped
inside the crystal lattices of metals. The principal physical and chemical characteristics of these
compounds are as follows:
(i) They have high melting points, higher than those of pure metals.
(ii) They are very hard, some borides approach diamond in hardness.
(iii) They retain metallic conductivity.
(iv) They are chemically inert.
Alloy Formation
An alloy is a blend of metals prepared by mixing the 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. The alloys so formed are hard and have often high melting points. The best
known are ferrous alloys: chromium, vanadium, tungsten, molybdenum and manganese are
used for the production of a variety of steels and stainless steel. Alloys of transition metals with
non transition metals such as brass (copper-zinc) and bronze (copper-tin), are also of
considerable industrial importance.

Do yourself -1

1. Addition of non-metals like B and C to the interstitial sites of a transition metal results the
metal
(A) of more ductability (B) of less ductability
(C) less malleable (D) of more hardness

2. The ionisation energies of transition elements are

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

3. Transition elements having more tendency to form complex than representative elements (s
and p-block elements) due to
(A) availability of d-orbitals for bonding
(B) variable oxidation states are not shown by transition elements
(C) all electrons are paired in d-orbitals
(D) f-orbitals are available for bonding

4. The metal(s) which does/do not form amalgam is/are

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

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

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(Organic Chemistry) d-BLOCK ELEMENTS
CHROMATE – DICHROMATE

Preparation:
(chromite ore)
[Lime (CaO) added with Na2 CO3 which keeps the mass porous so that air has access to all parts
and prevents fusion]
Then, 2Na2 CrO4 + H2 SO4 ⟶ Na2 SO4 ↓ +Na2 Cr2 O7 + H2 O
Its solubility Hence, suitable temp. is to be
Conc. Upto 32 C increases }
∘ Employed to crystallise out
And then decreases Na2 SO4 first.
Then Na2 Cr2 O7 is crystallised out as Na2 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.
2CrO2− + 2−
4 + 2H → Cr2 O7 + H2 O
Cr2 O2− − 2−
7 + 2OH → 2CrO4 + H2 O

The structures of chromate ion, CrO4 2− and the dichromate ion, Cr2 O7 2− are shown below. The
chromate ion is tetrahedral whereas the dichromate ion consists of two tetrahedra sharing one
corner with Cr − O − Cr bond angle of 126∘ . Sodium and potassium dichromates are strong
oxidising agents; the sodium salt has a greater solubility in water and is extensively used as an
oxidising agent in organic chemistry. Potassium dichromate is used as a primary standard in
volumetric analysis. In acidic solution, its oxidising action can be represented as follows:
Cr2 O2− + −
7 + 14H + 6e → 2Cr
3+
+ 7H2 O(E Θ = 1.33 V)

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(Organic Chemistry) d-BLOCK ELEMENTS
Thus, acidified potassium dichromate will oxidise iodides to iodine, sulphides to sulphur, tin
(II) to tin (IV) and iron(II) salts to iron(III). The half-reactions are noted below:

6I− → 3I2 + 6e− ; 3Sn2+ → 3Sn4+ + 6e−

3H2 S → 6H + + 3 S + 6e− ; 6Fe2+ → 6Fe3+ + 6e−

The full ionic equation may be obtained by adding the half-reaction for potassium dichromate
to the half-reaction for 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− 2−
4 , S2 O7 , Cr ⟶ CrO4 , Cr2 O7
(iii) CrO4−2 &SO2−4 are isomorphous
OH−
(iv) SO2 Cl2 &CrO2 Cl2 ⟶ SO2−
4 &CrO4 respectively.
2−
OH−
(v) SO3 Cl− &CrO3 Cl− ⟶ SO2−
4 &CrO4
2−

(vi) CrO3 &β(SO3 ) has same structure

Q. In laboratory 𝐊 𝟐 𝐂𝐫𝟐 𝐎𝟕 is used mainly not 𝐍𝐚𝟐 𝐂𝐫𝟐 𝐎𝟕 . Why?

Sol. Na2 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.
Q. How to standardise 𝐍𝐚𝟐 𝐒𝟐𝐎𝟑 solution in iodometry?
Sol. K 2 Cr2 O7 is primary standard ⇒ strength is known by weighing the salt in chemical
balance and dissolving in measured amount of water.
Then in acidic solution add. KI

Cr2 O2− +
7 + 14H + 6 F ⟶ 2Cr
3+
+ 3I2 + 7H2 O

This I2 is liberated can be estimated with S2 O3 2− .

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MANAGANATE & PERMANGANATE
PREPARATION OF MANGANATE (MnO2−
4 ) :-

In presence of KClO3 &KNO3 the above reaction is more faster because these two on
decomposition provides O2 easily.
Manganate is also obtained when KMnO4 is boiled with KOH.
boiled
4KMnO4 + 4KOH ⟶ 4 K 2 MnO4 + 2H2 O + O2
Properties: The above green solution is quite stable in alkali, but in pure water and in
presence of acids, depositing MnO2 and giving a purple solution of permanganate.
3 K 2 MnO4 + 2H2 O ⟶ 2KMnO4 + MnO2 ↓ +4KOH
0
prob. : EMnO 2 −MnO = 2.26 V; EMnO2 /MnO− = 0.56 V
2 2 4
2
Prove that MnO2−
4 will disproportionate in acidic medium.
Conversion of 𝐌𝐧𝐎𝟐−𝟒 to 𝐌𝐧𝐎𝟒
−

3 K 2 MnO4 + 2H2 SO4 ⟶ 2KMnO4 + MnO2 ↓ +2 K 2 SO4 + 2H2 O

or 3 K 2 MnO4 + 2H2 O + 4CO2 ⟶ 2KMnO4 + MnO2 + 4KHCO3
1
But in the above method 3 of Mn is lost as MnO2 but when 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
OR

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Oxidising Prop. of 𝐊𝐌𝐧𝐎𝟒 : (in acidic medium)
(i) MnO−4 + Fe
+2
+ H + ⟶ Fe+3 + Mn+2 + H2 O
(ii) MnO− +
4 + Γ + H ⟶ Mn
+2
+ I2 + H2 O
(iii) MnO4 + H2 O2 + H ⟶ Mn+2 + O2 + H2 O
− +

H⊕
(iv) MnO− 4 + SO2 ⟶ Mn
+2
+ H2 SO4
(v) MnO4 + NO2 + H ⟶ Mn+2 + NO−
− − +
3 + H2 O
(vi) MnO4 + H2 C2 O4 + H ⟶ Mn + CO2 + H2 O
− + +2

(vii) MnO− 4 + H2 S ⟶ Mn
2+
+ S ↓ +H2 O
(viii) MnO4 + S2 O3 ⟶ Mn + S ↓ +SO2−
− 2− 2+
4
(1) It is not a primary standard since it is difficult to get it in 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

4MnO− +
4 + 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.

4 + 2OH ⟶ 2MnO4 + H2 O + O. Then 2MnO4 + 2H2 O ⟶ 2MnO2 + 4OH + 2O

2MnO− − 2− 2− −

(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:

8MnO− 2− 2−
4 + 3 S2 O3 + H2 O ⟶ 8MnO2 + 6SO4 + 2OH
−

Oxidising Prop. in neutral or weakly acidic solution:

in presence Zn+2 or ZnO
(i) 2KMnO4 + 3MnSO4 + 2H2 O ⟶ 5MnO2 + K 2 SO4 + 2H2 SO4

or MnO− 4 + Mn
+2
+ 2H2 O ⟶ 5MnO2 + 4H +
In absence of Zn+2 ions, some of the Mn+2 ion may escape, oxidation through the
formation of insoluble MnII [MnIV O3 ] manganous permanganite.
Uses of 𝐊𝐌𝐧𝐎𝟒 :
Besides its use in analytical chemistry, potassium permanganate is used as a best oxidant in
preparative organic chemistry. Its uses for the bleaching of wool, cotton, silk and other textile
fibres and for the decolourisation of oils are also dependent on its strong oxidising power.
In laboratory conversion of Mn+2 to MnO4 − is done by :
(i) PbO2 (ii) Pb3 O4 + HNO3 (iii) Pb2 O3 + HNO3 (iv) NaBiO3 /H +

(v) (NH4 )2 S2 O8 /H + (vi) KIO4 /H +

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(Organic Chemistry) d-BLOCK ELEMENTS
Heating effect:

SILVER AND ITS COMPOUND

(I)

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.
4Ag + 8KCN + 2H2 O + O2 ⟶ 4 K[Ag(CN)2] + 4KOH
AgNO3
Preparation: Reaction of Ag with dilute HNO3 or conc. HNO3 .
Properties:
(i) It is called as lunar caustic because in contact with skin it produces burning sensation like
that of caustic soda with the formation of finely divided silver (black colour)
(ii) Thermal decomposition :
(iii) Props. of AgNO3
6AgNO3 + 3I2 + 3H2 O ⟶ 5AgI + AgIO3 + 6HNO3
(excess)
Δ
(iv) Ag 2 SO4 ⟶ 2Ag + SO2 + O2

Δ
(vi) Ag 2 S2 O3 + H2 O ⟶ Ag 2 S + H2 SO4
AgCl, AgBr, AgI (but not Ag 2 S ) are soluble in Na2 S2 O3 forming [Ag(S2 O3 )2 ]−3 complexes
KBr
(vii) AgBr + AgNO3 ⟶ AgBr ↓ +KNO3
Pale yellow
ppt.

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(Organic Chemistry) d-BLOCK ELEMENTS
212∘ C
Heating effect: 2AgNO3 ⟶ 2AgNO2 + O2
500∘ C
2AgNO2 ⟶ 2Ag + 2NO + O2
(viii)

Ag 2 O + H2 O2 ⟶ 2Ag + H2 O + O2
K 2 S2 O8 + 2AgNO3 + 2H2 O ⟶ 2AgO + 2KHSO4 + 2HNO3
AgO supposed to be paramagnetic due to d9 configuration. 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 appearance
Preparation: [1] 2 Zn + O2 ⟶ 2ZnO
[2] Calcination of ZnCO3 or Zn(NO3 )2 or Zn(OH)2
Purest 𝐙𝐧𝐎: 4ZnSO4 + 4Na2 CO3 + 3H2 O ⟶ ZnCO3 ⋅ 3Zn(OH)2 ↓ +4Na2 SO4 + 3CO2

Δ
Properties: [1] ZnO( cold ) ⇄ ZnO( hot )
white yellow
[2] It is insoluble in water
[3] It sublimes at 400∘ C
[4] It is amphoteric oxide , react with acid & base both.
ZnO + 2HCl ⟶ ZnCl2 + H2 O
ZnO + H2 SO4 ⟶ ZnSO4 + H2 O
ZnO + 2NaOH ⟶ Na2 ZnO2 + H2 O

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[5] ZnO ⟶ Zn by H2 &C
>400∘ C
ZnO + H2 ⟶ Zn + H2 O
ZnO + C ⟶ Zn + CO
[6] It forms Rinmann's green with Co(NO3 )2
2Co(NO3 )2 ⟶ 2CoO + 4NO2 + O2
CoO + ZnO ⟶ CoZnO2 or CoO ⋅ ZnO
Rinmann's green
Uses: (1) As white pigment, it is superior than white lead because it does not turn into black
(2) Rinmann's green is used as green pigment
(3) It is used as zinc ointment in medicine
𝐙𝐧𝐂𝐥𝟐
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
or Zn + HgCl2 ⟶ ZnCl2 + Hg
Properties: (i) It is deliquescent white solid (when anhydrous)
(ii) ZnCl2 + H2 S ⟶ ZnS
excess
“ +NaOH ⟶ Zn(OH)2 ⟶ Na2 [Zn(OH)4 ]
excess
“ +NH4 OH ⟶ Zn(OH)2 ⟶ [Zn(NH)4 ]2+
Uses: [1] Used for impregnating timber to prevent destruction by insects
[2] As dehydrating agent when anhydrous
[3] ZnO ⋅ ZnCl2 used in dental filling

𝐙𝐧𝐒𝐎4
𝐏𝐫𝐞𝐩𝐚𝐫𝐚𝐭𝐢𝐨𝐧: ⎯→ Zn + dil H2 SO4 ⟶ ZnSO4 + H2
ZnO + dil H2 SO4 ⟶ ZnSO4 + H2 O
ZnCO3 + dil H2 SO4 ⟶ ZnSO4 + H2 O + CO2
Zn2O2 ⟶ ZnSO
3 } Parallel reaction
ZnS + 2 O2 ⟶ ZnO + SO2
ZnS + 4O3 ⟶ ZnSO4 4O2

39−70∘ C >70∘ C >280∘ C

Properties: ZnSO4 ⋅ 7H2 O ⟶ ZnSO4 ⋅ 6H2 O ⟶ ZnSO4 ⋅ H2 O ⟶ ZnSO2

APNI KAKSHA 13
(Organic Chemistry) d-BLOCK ELEMENTS
Uses: [1] in eye lotion
[2] Lithophone making (ZnS + BaSO4 ) as white pigment
COPPER COMPOUNDS
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 + 2 O2 ⟶ 2CuO
Δ
(iii) Cu(OH)2 ⟶ CuO + H2 O
250∘ C
(iv) 2Cu(NO3 )2 ⟶ 2CuO + 4NO2 + O2
Properties: (i) CuO is insoluble in water
(ii) Readily dissolves in dil. Acids
CuO + H2 SO4 ⟶ CuSO4 + H2 O
HCl ⟶ CuCl2
HNO3 ⟶ Cu(NO3 )2
(iii) It decomposes when, heated above 1100∘ C
4CuO ⟶ 2Cu2 O + O2
(iv) CuO is reduced to Cu by H2 or C under hot condition
CuO + C ⟶ Cu + CO ↑
CuO + H2 ⟶ Cu + H2 O ↑
𝐂𝐮𝐂𝐥𝟐
Preparation: → CuO + 2HCl (conc.) ⟶ CuCl2 + H2 O
Cu(OH)2 ⋅ CuCO3 + 4HCl ⟶ 2CuCl2 + 3H2 O + CO2
Properties: → (i) It is crystallised as CuCl2 ⋅ 2H2 O of Emerald green colour
(ii) dil. solution in water is blue in colour due to formation of [Cu(H2 O)4 ]2+
complex.
(iii) conc. HCl or KCl added to dil. solution of CuCl2 the colour changes into
yellow, owing to the formation of [CuCl4 ]2−
(iv) The conc. aq. solution is green in colour having the two complex ions in
equilibrium 2[Cu(H2 O)4 ]Cl2 ⇌ [Cu(H2 O)4 ]2+ + [CuCl4 ]2− + 4H2 O
(v) CuCl2 ⟶ CuCl by no. of reagents
Δ
(a) CuCl2 + Cu-turnings ⟶ 2CuCl
(b) 2CuCl2 + H2 SO3 + H2 O ⟶ 2CuCl + 2HCl + 2H2 SO4
(c) 2CuCl2 + Zn/HCl ⟶ 2CuCl + ZnCl2
(d) CuCl2 + SnCl2 ⟶ CuCl + SnCl4
CuF3 ⋅ 2H2 O ⟶ light blue Anh. CuCl2 is dark brown mass obtained
CuCl2 ⋅ 2H2 O ⟶ green { By heating CuCl2 ⋅ 2H2 O at 150∘ C in presence
CuBr2 ⟶ almost black of HCl vap.
150∘ C
CuI2 does not exit CuCl2 ⋅ 2H2 O ⟶ CuCl2 + 2H2 O
HCl gas

APNI KAKSHA 14
(Organic Chemistry) d-BLOCK ELEMENTS
Preparation: → CuSO4
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 + 2 O2 ⟶ CuSO4 + H2 O [Commercial scale]
(Scrap)
Cu + dil. H2 SO4 ⟶ no reaction {Cu is a below H in electrochemical series }
Properties: → (i) It is crystallised as CuSO4 ⋅ 5H2 O

(iii) Revision with all others reagent

IRON COMPOUNDS
𝐅𝐞𝐒𝐎𝟒 ⋅ 𝟕𝐇𝟐 𝐎
Preparation: → (i) Scrap Fe + H2 SO4 ⟶ FeSO4 + H2 ↑
(dil.)
(ii) From Kipp's waste
FeS + H2 SO4 ( dil) ⟶ FeSO4 + H2 S ↑
7
(iii) FeS2 + 2H2 O + 2 O2 ⟶ FeSO4 + H2 SO4
Properties: → (i) It undergoes aerial oxidation forming basic ferric sulphate
4FeSO4 + H2 O + O2 ⟶ 4Fe(OH)SO4
300∘ C temp.
(ii) FeSO4 ⋅ 7H2 O ⟶ FeSO4 ⟶ Fe2 O3 + SO2 + SO3
high
anh.white
(iii) Aq. solution is acidic due to hydrolysis
FeSO4 + 2H2 OlFe(OH)2 + H2 SO4
weak base
(iv) It is a reducing agent
(a) Fe2+ + MnO− +
4 + H ⟶ Fe
3+
+ Mn2+ + H2 O
(b) Fe2+ + CrO2− +
7 + H ⟶ Fe
3+
+ Cr 3+ + H2 O
(c) Au3+ + Fe2+ ⟶ Au + Fe3+
(d) Fe2+ + HgCl2 ⟶ Hg 2 Cl2 ↓ +Fe3+
white ppt.
(v) It forms double salt. Example (NH4 )2 SO4 ⋅ FeSO4 ⋅ 6H2 O

APNI KAKSHA 15
(Organic Chemistry) d-BLOCK ELEMENTS
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
DO YOURSELF – 2
1.
(A) X = OH − , Y = H + (B) X = H + , Y = OH −
(C) X = OH − , Y = H2 O2 (D) X = H2 O2 , Y = OH −

Org.solvent
2. Acidified chromic acid +H2 O2 ⟶ X + Y, X and Y are (blue colour)
(A) CrO5 and H2 O (B) Cr2 O3 and H2 O
(C) CrO2 and H2 O (D) CrO and H2 O

3. Cu + conc. HNO3 ⟶ Cu(NO3 )2 + X (oxide of nitrogen); then X is (hot)

(A) N2 O (B) NO2 (C) NO (D) N2 O3

4. CuSO4 solution reacts with excess KCN to give

(A) Cu(CN)2 (B) CuCN (C) K 2 [Cu(CN)2 ] (D) K 3 [Cu(CN)4 ]

5. In the equation: M + 8CN− + 2H2 O + O2 ⟶ 4[M(CN)2 ]− + 4OH − , metal M is

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

APNI KAKSHA 16
(Organic Chemistry) d-BLOCK ELEMENTS
EXERCISE-I
Select one or more than one correct options.
Q.1 (T) imparts violet colour in the flame test

NH3 soln.
(W)Red ppt. ⟶ (X)
dil HCl
(W)Red ppt. ⟶ (Y)white ppt.
NaOH
Δ
(U) ⟶ (Z)gas (gives white fumes with HCl )
sublimes on heating
Identify (𝐓) to (𝐙).
(A) T = KMnO4 , U = HCl, V = Cl2 , W = HgI2 , X = Hg(NH2 )NO3 , Y = Hg 2 Cl2 , Z = N2
(B) T = K 2 Cr2 O7 , U = NH4 Cl, V = CrO2 Cl2 , W = Ag 2 CrO4 , X = [Ag(NH3 )2 ]+ , Y = AgCl, Z = NH3
(C) T = K 2 CrO4 , U = KCl, V = CrO2 Cl2 , W = HgI2 , X = Na2 CrO4 , Y = BaCO3 , Z = NH4 Cl
(D) T = K 2 MnO4 , U = NaCl, V = CrO3 , W = AgNO2 , X = (NH4 )2 CrO4 , Y = CaCO3 , Z = SO2

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

Fe+Mo
Q.3 N2 ( g) + 3H2 ( g) ⇌ 2NH3 ( g); Haber's process, Mo is used as
(A) a catalyst (B) a catalytic promoter
(C) an oxidising agent (D) as a catalytic poison

Q.4 Potash alum is a double salt, its aqueous solution shows the characteristics of
(A) Al3+ ions (B) K + ions (C) SO4 2− ions (D) Al3+ ions but not K + ions

Q.5 Mercury is a liquid at 0∘ C because of

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

Q.6 CrO3 dissolves in aqueous NaOH to give

(A) Cr2 O2−
7 (B) CrO4 2− (C) Cr(OH)3 (D) Cr(OH)2

Q.7 The correct statement(s) about transition elements is/are

(A) the most stable oxidation state is +3 and its stability decreases across the period
(B) transition elements of 3 d-series have almost same atomic sizes from Cr to Cu
(C) the stability of +2 oxidation state increases across the period
(D) some transition elements like Ni, Fe, Cr may show zero oxidation state in some of their
compounds

APNI KAKSHA 17
(Organic Chemistry) d-BLOCK ELEMENTS
Q.8 An ornamental of gold having 75% of gold, it is of carat.
(A) 18 (B) 16 (C) 24 (D) 20

Q.9 Solution of MnO− 4 is purple-coloured due to

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

Q.10 During estimation of oxalic acid Vs KMnO4 , self indicator is

(A) KMnO4 (B) oxalic acid (C) K 2 SO4 (D) MnSO4

Q.11 Which of the following statements concern with transition metals?

(A) compounds containing ions of transition elements are usually coloured
(B) Zinc has lowest melting point among 3d-series elements
(C) they show variable oxidation states, which differ by two units only
(D) they easily form complexes

Q.12 Correct statement(s) is/are

(A) an acidified solution of K 2 Cr2 O7 liberates iodine from KI
(B) K 2 Cr2 O7 is used as a standard solution for estimation of Fe2+ ions
(C) in acidic medium, M = N/6 for K 2 Cr2 O7
(D) (NH4 )2 Cr2 O7 on heating decomposes to yield Cr2 O3 through an endothermic reaction

Q.13 The highest oxidation state among transition elements is

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

Q.14 A compound of mercury used in cosmetics, in Ayurvedic and Yunani medicines and known as
Vermilon is
(A) HgCl2 (B) HgS (C) Hg 2 Cl2 (D) HgI

KI dil 2 SO4
Q.15 ↑ Y(g) ⟵ CuSO4 ⟶ X (Blue colour), X and Y are
(A) X = I2 , Y = [Cu(H2 O)4 ]2+ (B) X = [Cu(H2 O)4 ]2+ , Y = I2
(C) X = [Cu(H2 O)4 ]+ , Y = I2 (D) X = [Cu(H2 O)5 ]2+ , Y = I2

Q.16 (NH4 )2 Cr2 O7 (Ammonium dichromate) is used in fireworks. The green coloured powder blown
in air is
(A) Cr2 O3 (B) CrO2 (C) Cr2 O4 (D) CrO3

Q.17 The d-block element which is a liquid at room temperature, having high specific heat, less
reactivity than hydrogen and its chloride (MX 2 ) is volatile on heating is
(A) Cu (B) Hg (C) Ce (D) Pm

APNI KAKSHA 18
(Organic Chemistry) d-BLOCK ELEMENTS
Q.18 Coinage metals show the properties of
(A) typical elements (B) normal elements
(C) inner-transition elements (D) transition element

Q.19 Iron becomes passive by…………. due to formation of……………..

(A) dil. HCl, Fe2 O3 (B) 80% conc. HNO3 , Fe3 O4
(C) conc. H2 SO4 , Fe3 O4 (D) conc. HCl, Fe3 O4

Q.20 Bayer's reagent used to detect olefinic double bond is

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

Q.21 Amphoteric oxide(s) is/are

(A) Al2 O3 (B) SnO (C) ZnO (D) Fe2 O3

Q.22 Interstitial compounds are formed by

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

Q.23 The transition metal used in X-rays tube is

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

Q.24 The catalytic activity of transition elements is related to their

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

Q.25

x, y and z are respectively

(A) 1,2,3 (B) 1,5,3 (C) 1,3,5 (D) 5,3,1

Q.26 When KMnO4 solution is added to hot oxalic acid solution, the decolourisation is slow in the
beginning but becomes instantaneous after some time. This is because
(A) Mn2+ acts as auto catalyst (B) CO2 is formed
(C) Reaction is exothermic (D) MnO− 4 catalyses the reaction.

Q.27 The higher oxidation states of transition elements are found to be in the combination with A
and B, which are
(A) F, O (B) O, N (C) O, Cl (D) F, Cl

APNI KAKSHA 19
(Organic Chemistry) d-BLOCK ELEMENTS
Q.28 An element of 3d-transition series shows two oxidation states x and y, differ by two units then
(A) compounds in oxidation state x are ionic if x > y
(B) compounds in oxidation state x are ionic if x < y
(C) compounds in oxidation state y are covalent if x < y
(D) compounds in oxidation state y are covalent if y < x

Q.29 Pick out the incorrect statement:

(A) MnO2 dissolves in conc. HCl, but does not form Mn4+ ions
(B) MnO2 oxidizes hot concentrated H2 SO4 liberating oxygen
(C) K 2 MnO4 is formed when MnO2 in fused KOH is oxidised by air, KNO3 , PbO2 or NaBiO3
(D) Decomposition of acidic KMnO4 is not catalysed by sunlight.

Q.30 1 mole of Fe2+ ions are oxidised to Fe3+ ions with the help of (in acidic medium)
(A) 1/5 moles of KMnO4 (B) 5/3 moles of KMnO4
(C) 2/5 moles of KMnO4 (D) 5/2 moles of KMnO4

Q.31 The metals present in insulin and haemoglobin are respectively

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

Q.32 To an acidified dichromate solution, a pinch of Na2 O2 is added and shaken. What is observed:
(A) blue colour (B) Orange colour changing to green
(C) Copious evolution of oxygen (D) Bluish - green precipitate

Q.33 The rusting of iron is formulated as Fe2 O3 ⋅ xH2 O which involves the formation of
(A) Fe2 O3 (B) Fe(OH)3 (C) Fe(OH)2 (D) Fe2 O3 + Fe(OH)3

Q.34 Metre scales are made-up of alloy

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

Q.35 Amongst CuF2 , CuCl2 and CuBr2

(A) only CuF2 is ionic
(B) both CuCl2 and CuBr2 are covalent
(C) CuF2 and CuCl2 are ionic but CuBr2 is covalent
(D) CuF2 , CuCl2 as well as CuBr2 are ionic

Q.36 A metal M which is not affected by strong acids like conc. HNO3 , conc. H2 SO4 and conc. solution
of alkalis like NaOH, KOH forms MCl3 which finds use for toning in photography. The metal M is
(A) Ag (B) Hg (C) Au (D) Cu

Q.37 Solid CuSO4 ⋅ 5H2 O having covalent, ionic as well as co-ordinate bonds. Copper atom/ion forms
co-ordinate bonds with water.
(A) 1 (B) 2 (C) 3 (D) 4

APNI KAKSHA 20
(Organic Chemistry) d-BLOCK ELEMENTS
Q.38 CuSO4 (aq) + 4NH3 ⟶ X, then X is
(A) [Cu(NH3 )4 ]2+ (B) paramagnetic
(C) Coloured (D) of a magnetic moment of 1.73BM

Q.39 KMnO4 + HCl ⟶ H2 O + X(g), X is a (acidified)

(A) red liquid (B) violet gas
(C) greenish yellow gas (D) yellow-brown gas

Q.40 Purple of Cassius is:

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

Q.41 Amongst the following species, maximum covalent character is exhibited by

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

Q.42 Number of moles of SnCl2 required for the reduction of 1 mole of K 2 Cr2 O7 into Cr2 O3 is
(in acidic medium)
(A) 3 (B) 2 (C) 1 (D) 1/3

Q.43 Amphoteric oxide(s) of Mn is/are

(A) MnO2 (B) Mn3 O4 (C) Mn2 O7 (D) MnO

Q.44 Pick out the incorrect statement:

(A) MnO2−4 is quite strongly oxidizing and stable only in very strong alkalies. In dilute
alkali,neutral solutions, it disproportionates.
(B) In acidic solutions, MnO− 4 is reduced to Mn
2+
and thus, KMnO4 is widely used as oxidising
agent
(C) KMnO4 does not acts as oxidising agent in alkaline medium
(D) KMnO4 is manufactured by the fusion of pyrolusite ore with KOH in presence of air or
KNO3 , followed by electrolytic oxidation in strongly alkaline solution.

Q.45 The aqueous solution of CuCrO4 is green because it contains

(A) green Cu2+ ions (B) green CrO4 2− ions
(C) blue Cu2+ ions and green CrO2−
4 ions (D) blue Cu2+ ions and yellow CrO4 2− ions

Q.46 Manganese steel is used for making railway tracks because

(A) it is hard with high percentage of Mn
(B) it is soft with high percentage of Mn
(C) it is hard with small concentration of manganese with impurities
(D) it is soft with small concentration of manganese with impurities

APNI KAKSHA 21
(Organic Chemistry) d-BLOCK ELEMENTS
Q.47 In nitroprusside ion, the iron exists as Fe2+ and NO as NO+ rather than Fe3+ and NO
respectively. These forms of ions are established with the help of
(A) Magnetic moment in solid state (B) thermal decomposition method
(C) by reaction with KCN (D) by action with K 2 SO4

Q.48 Acidified KMnO4 can be decolourised by

(A) SO2 (B) H2 O2 (C) FeSO4 (D) Fe2 (SO4 )3

Q.49 Transition elements in lower oxidation states act as Lewis acid because
(A) they form complexes (B) they are oxidising agents
(C) they donate electrons (D) they do not show catalytic properties

Q.50 The lanthanide contraction is responsible for the fact that

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

Q.51 The Ziegler-Natta catalyst used for polymerisation of ethene and styrene is TiCl4 + (C2 H5 )3 Al,
the catalysing species (active species) involved in the polymerisation is
(A) TiCl4 (B) TiCl3 (C) TiCl2 (D) TiCl

Q.52 Ion(s) having non zero magnetic moment (spin only) is/are
(A) Sc 3+ (B) Ti3+ (C) Cu2+ (D) Zn2+

Q.53 The electrons which take part in order to exhibit variable oxidation states by transition metals
are
(A) ns only (B) (n − 1)d only
(C) ns and (n-1)d only but not np (D) (n-1)d and np only but not ns

Q.54 'Bordeaux mixture' is used as a fungicide. It is a mixture of

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

Q.55 Which of the following reaction is possible at anode?

(A) 2Cr 3+ + 7H2 O ⟶ Cr2 O2−
7 + 14H
+
(B) F2 ⟶ 2 F −
1
(C) 2 O2 + 2H + ⟶ H2 O (D) None of these

Q.56 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

Q.57 Peacock ore is:

(A) FeS2 (B) CuFeS2 (C) CuCO3 (D) Cu(OH)2

APNI KAKSHA 22
(Organic Chemistry) d-BLOCK ELEMENTS
Q.58 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) MnO− 4 catalyses the reaction

Question No. 59 to 68
Questions given below consist of two statements each printed as Assertion (A) and Reason (R);
while answering these questions you are required to choose any one of the following four
responses:
(A) if both (A) and (R) are true and (R) is the correct explanation of (A)
(B) if both (A) and (R) are true but (R) is not correct explanation of (A)
(C) if (A) is true but (R) is false
(D) if (A) is false and (R) is true
Q.59 Assertion: KMnO4 is purple in colour due to charge transfer.
Reason: In MnO− 4 , there is no electron present in d-orbitals of manganese.

Q.60 Assertion: K 2 CrO4 has yellow colour due to charge transfer.

Reason: CrO2−
4 ion is tetrahedral in shape.

Q.61 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.

Q.62 Assertion: CrO3 reacts with HCl to form chromyl chloride gas.
Reason: Chromyl chloride (CrO2 Cl2 ) has tetrahedral shape.

Q.63 Assertion: Zinc does not show characteristic properties of transition metals.
Reason: In zinc outermost shell is completely filled.

Q.64 Assertion: Tungsten has a very high melting point.

Reason: Tungsten is a covalent compound.

Q.65 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 .

Q.66 Assertion: Ce4+ is used as an oxidising agent in volumetric analysis.

Reason: Ce4+ has the tendency of attain +3 oxidation state.

Q.67 Assertion: Promethium is a man made element.

Reason: It is radioactive and has been prepared by artificial means.

Q.68 Assertion: Cu+ ion is colourless.

Reason: Four water molecules are coordinated to Cu+ ion in water.
APNI KAKSHA 23
(Organic Chemistry) d-BLOCK ELEMENTS
EXERCISE-II
JEE-MAIN
1. Number of electrons transferred in each case when KMnO4 acts as an oxidising agent to give
MnO2 , Mn2+ , Mn(OH)3 and MnO4 2− are respectively : [AIEEE 2002, 3/225]
(A) 3,5,4 and 1 (B) 4,3,1 and 5
(C) 1,3,4 and 5 (D) 5,4,3 and 1

2. Which of the following ions has the maximum magnetic moment? [AIEEE 2002, 3/225]
(A) Mn 2+
(B) Fe 2+
(C) Ti 2+
(D) Cr .
2+

3. Most common oxidation state fo Ce (Cerium) are : [AIEEE 2002, 3/225]

(A) +3, +4 (B) +2, +3 (C) +2, +4 (D) +3, +5

4. What would happen when a solution of potassium chromate is treated with an excess of dilute
HNO3 ? [AIEEE 2003, 3/225]
(A) Cr2 O7 and H2 O are formed
2−
(B) CrO4 is reduced to +3 state of Cr
2−

(C) CrO4 is oxidised to +7 state of Cr

2−
(D) Cr 3+ and Cr2 O2−
7 are formed

5. Which one of the following nitrates will leaves behind a metal on strong heating ?
[AIEEE 2003, 3/225]
(A) Copper nitrate (B) Manganese nitrate
(C) Silver nitrate (D) Ferric nitrate

6. The atomic numbers of V, Cr, Mn and Fe are respectively 23,24,25 and 26 . Which one of these
may be expected to have the highest second ionization enthalpy? [AIEEE 2003, 3/225]
(A) Cr (B) Mn (C) Fe (D) V

7. Which of the following group of transition metals is called coinage metals ?

[AIEEE 2003, 3/225]
(A) Cu, Ag, Au (B) Ru, Rh, Pb (C) Fe, Co, Ni (D) Os. Ir, Pt

8. The number of d-electrons retained in Fe2+ (At. no. Fe = 26 ) ions are: [AIEEE 2003, 3/225]
(A) 3 (B) 4 (C) 5 (D) 6

9. Ammonia forms the complex ion [Cu(NH3 )4 ]2+ with copper ions in the alkaline solutions but
not in acidic solutions. What is the Statement-2 for it? [AIEEE 2003, 3/225]
(A) In acidic solutions hydration protects copper ions
(B) In acidic solutions protons co-ordinate with ammonia molecules forming NH4 + ions and
NH3 molecules are not available.
(C) In alkaline solutions insoluble Cu(OH)2 is precipitated which is soluble in excess of any
alkali
(D) Copper hydroxide is an amphoteric substance.

APNI KAKSHA 24
(Organic Chemistry) d-BLOCK ELEMENTS
10. The radius of La3+ (Atomic number of La = 57 ) is 1.06Å. Which one of the following given
values will be closest to the radius of Lu3+ (Atomic number of Lu = 71 )?
[AIEEE 2003, 3/225]
(A) 1.60Å (B) 1.40Å (C) 1.06Å (D) 0.85Å

11. Cerium (Z = 58) is an important member of the lanthanoide. Which of the following statement
about cerium is incorrect? [AIEEE 2004, 3/225]
(A) The common oxidation state of cerium are +3 and +4 .
(B) The +3 oxidation state of cerium is more stable than +4 oxidation state.
(C) The +4 oxidation state of cerium is not known in solution.
(D) Cerium (IV) acts as an oxidizing agent.

12. The lanthanide contraction is responsible for the fact that [AIEEE 2005, 3/225]
(A) Zr and Y have about the same radius
(B) Zr and Nb have similar oxidation state
(C) Zr and Hf have about the same radius
(D) Zr and Zn have same oxidation state.

13. Which of the following factors may be regarded as the main cause of lanthanide contraction ?
[AIEEE 2005, 41/2/225]
(A) Greater shielding of 5 d electrons by 4f electrons
(B) Poorer shielding of 5 d electron by 4f electrons
(C) Effective shielding of one of 4f electrons by another in the sub-shell
(D) Poor shielding of one of 4f electron by another in the sub-shell.

14. The "spin-only"' magnetic moment [in units of Bohr magneton, (μB ) of Ni2+ in aqueous solution
would be (atomic number of Ni = 28 ) [AIEEE 2006, 3/165]
(A) 2.84 (B) 4.90 (C) 0 (D) 1.73

15. Lanthanoid contraction is caused due to: [AIEEE 2006, 3/165]

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

16. Identify the incorrect statement among the following. [AIEEE 2007, 3/120]
(A) The chemistry of various lanthanoids is very similar.
(B) 4f and 5 forbitals are equally shielded.
(C) d-block elements show irregular and erratic chemical properties among themselves.
(D) La and Lu have partially filled d orbitals and no other partially filled orbitals.

APNI KAKSHA 25
(Organic Chemistry) d-BLOCK ELEMENTS
17. The actinoids exhibit more number of oxidation states in general than the lanthanoids. This is
because [AIEEE 2007, 3/120]
(A) The actinoids are more reactive than the lanthanoids.
(B) The 5 forbitals extend farther from the nucleus than the 4 orbitals.
(C) The 5 f orbitals are more buried than the 4 forbitals
(D) There is a similarity between 4f and 5f orbitals in their angular part of the wave function

18. Larger number of oxidation states are exhibited by the actinoids than those by the lanthanoids,
the main reason being. [AIEEE 2008, 3/105]
(A) lesser energy difference between 5f and 6 d than between 4f and 5 d orbitals
(B) more energy difference between 5f and 6 d than between 4f and 5 d orbitals
(C) more reactive nature of the actinoids than the lanthanoids
(D) 4f orbitals more diffused than the 5 forbitals

19. In context with the transition elements, which of the following statements is incorrect?
[AIEEE 2009, 4/144]
(A) In the highest oxidation states, the transition metal show basic character and form cationic
complexes.
(B) In the highest oxidation states of the first five transition elements ( Sc to Mn), all the 4 s and
3 d electrons are used for bonding.
(C) Once the d5 configuration is exceeded, the tendency to involve all the 3 d electrons in
bonding decreases.
(D) In addition to the normal oxidation states, the zero oxidation state is also shown by these
elements in complexes.

20. Knowing that the Chemistry of lanthanoids (Ln) is dominated by its +3 oxidation state, which
of the following statement is incorrect? [AIEEE 2009, 4/144]
(A) The ionic sizes of Ln (III) decrease in general with increasing atomic number.
(B) Ln (III) compounds are generally colourless.
(C) Ln (III) hydroxides are mainly basic in character
(D) Because of the large size of the Ln (III) ions the bonding in its compounds is predominently
ionic in character.

0
21. The correct order of EM 2+ /M values with negative sign for the four successive elements Cr, Mn,

Fe and Co is [AIEEE 2010, 4/144]

(A) Mn > Cr > Fe > Co (B) Cr > Fe > Mn > Co
(C) Fe > Mn > Cr > Co (D) Cr > Mn > Fe > Co

22. In context of the lanthanoids, which of the following statement is not correct?
[AIEEE 2011, 4/120]
(A) There is a gradual decrease in the radii of the members with increasing atomic number in
the series.
(B) All the member exhibit +3 oxidation state.
APNI KAKSHA 26
(Organic Chemistry) d-BLOCK ELEMENTS
(C) Because of similar properties the separation of lanthanoids is not easy.
(D) Availability of 4f electrons results in the formation of compounds in +4 state for all the
members of the series.

23. The outer electron configuration of Lu (Atomic No : 71) is : [AIEEE 2011, 4/120]
(A) 4f 3 5 d5 6 s 2 (B) 4f 8 5 d0 6 s 2 (C) 4f 4 5d4 6s2 (D) 4f 14 5 d1 6 s2

24. Iron exhibits +2 and +3 oxidation states. Which of the following statements about iron is
incorrect ? [AIEEE 2012, 4/120]
(A) Ferrous oxide is more basic in nature than the ferric oxide.
(B) Ferrous compounds are relatively more ionic than the corresponding ferric compounds
(C) Ferrous compounds are less volatile than the corresponding ferric compounds
(D) Ferrous compounds are more easily hydrolysed than the corresponding ferric compounds.

25. Which of the following arrangements does not represent the correct order of the property
stated against it? [JEE(Main) 2013, 4/120]
(A) V < Cr < Mn < Fe : paramagnetic behaviour
2+ 2+ 2+ 2+

(B) Ni2+ < Co2+ < Fe2+ < Mn2+ : ionic size
(C) Co3+ < Fe3+ < Cr 3+ < Sc 3+ : stability in aqueous solution
(D) Sc < Ti < Cr < Mn : number of oxidation states

26. Four successive members of the first row transition elements are listed below with atomic
0
numbers. Which one of them is expected to have the highest EM 3+ /M2+ value ?

[JEE(Main) 2013, 4/120]

(A) Cr (Z = 24) (B) Mn (Z = 25) (C) Fe(Z = 26) (D) Co (Z = 27)

27. Which series of reactions correctly represents chemical relations related to iron and its
compound? [JEE(Main) 2014, 4/120]
dill H2 SO4 H2 SO4 ,O2 heat
(A) Fe ⟶ FeSO4 ⟶ Fe2 (SO4 )3 ⟶ Fe
O2 , heat dill 2 SO4 heat
(B) Fe ⟶ FeO ⟶ FeSO4 ⟶ Fe
Cl2 , heat heat,air Zn
(C) Fe ⟶ FeCl3 ⟶ FeCl2 ⟶ Fe
O2 ,heat CO,600∘ C CO,700∘ C
(D) Fe ⟶ Fe3 O4 ⟶ FeO ⟶ Fe

28. The equation which is balanced and represents the correct product(s) is :
[JEE(Main) 2014, 4/120]
(A) Li2 O + 2KCl → 2LiCl + K 2 O
(B) [CoCl(NH3 )5 ]+ + 5H + → Co2+ + 5NH4+ + Cl−
excess, NaOH
(C) [Mg(H2 O)6 ]2+ + ( EDTA )4− ⟶ [Mg( EDTA )]2+ + 6H2 O
(D) CuSO4 + 4KCN → K 2 [Cu(CN)4 ] + K 2 SO4

APNI KAKSHA 27
(Organic Chemistry) d-BLOCK ELEMENTS
29. The colour of KMnO4 is due to : [JEE(Main) 2015, 4/120]
(A) M → L charge transfer transition (B) d − d transition
(C) L → M charge transfer transition (D) σ − σ∗ transition

30. When XO2 is fused with an alkali metal hydroxide in presence of an oxidizing agent such as
KNO3 ; a dark green product is formed which disproportionates in acidic solution to afford a
dark purple solution. X is : [JEE(Main) 2018(online)]
(A) Ti (B) V (C) Cr (D) Mn

31. The transition element that has lowest enthalpy of atomisation is : [JEE-Main 2019]
(A) Zn (B) Cu (C) Fe (D) V

32. Consider the following reduction processes : [JEE-Main 2019]

Zn2+ + 2e− → Zn(s); E o = −0.76 V
Ca2+ + 2e− → Ca(s); E o = −2.87 V
Mg 2+ + 2e− → Mg(s); E o = −2.36 V
Ni2+ + 2e− → Ni(s); E o = −0.25 V
The reducing power of the metals increases in the order :
(A) Ca < Mg < Zn < Ni (B) Zn < Mg < Ni < Ca
(C) Ni < Zn < Mg < Ca (D) Ca < Zn < Mg < Ni

33. The electrolytes usually used in the electroplating of gold and silver, respectively, are :
[JEE-Main 2019]
(A) [Au(CN2 )] and [Ag(CN)2 ]
− −
(B) [Au(NH3 )2] and [Ag(CN)2 ]−
+

(C) [Au(CN2 )]− and [Ag(Cl)2 ]− (D) [Au(OH)4 ]− and [Ag(OH)2 ]−

34. The element that usually does NOT show variable oxidation states is : [JEE-Main 2019]
(A) Cu (B) Sc (C) V (D) Ti

35. The correct order of the first ionization enthalpies is: [JEE-Main 2019]
(A) Ti < Mn < Zn < Ni (B) Ti < Mn < Ni < Zn
(C) Mn < Ti < Zn < Ni (D) Zn < Ni < Mn < Ti

36. Thermal decomposition of a Mn compound (X) at 513K results in compound Y, MnO2 and a
gaseous product MnO2 reacts with NaCl and concentrated H2 SO4 to give pungent gas Z. X, Y, and
Z, respectively, are: [Main April 12, 2019]

(A) KMnO4 , K 2 MnO4 and Cl2 (B) K 2 MnO4 , KMnO4 and SO2
(C) K 3 MnO4 , K 2 MnO4 and Cl2 (D) K 2 MnO4 , KMnO4 and Cl2

APNI KAKSHA 28
(Organic Chemistry) d-BLOCK ELEMENTS
37. Match the catalysts (Column-I) with products (Column-II) [Main April 9, 2019]
Column-1 Column-2
(Catalyst) (Product)
(A) V2 O5 (i) Polyethylene
(B) TiCl4 /Al(Me)3 (ii) ethanol
(C) PdCl2 (iii) H2SO4
(D) Iron Oxide (iv) NH3
(A) (A)-(iii); (B)-(iv); (C)-(i); (D)-(ii)
(B) (A)-(ii);(B)-(iii); (C)-(i); (D)-(iv)
(C) (A)-(iii); (B)-(i); (C)-(ii); (D)-(iv)
(D) (A)-(iv); (B)-(iii); (C)-(ii); (D)-(i)

38. The incorrect statement is: [Main Sep. 03, 2020]

(A) Manganate and permanganate ions are tetrahedral
(B) In manganate and permanganate ions, the π-bonding takes place by overlap of p-orbitals of
oxygen and d orbitals of manganese
(C) Manganate and permanganate ions are paramagnetic
(D) Manganate ion is green in colour and permanganate ion is purple in colour
39. The third ionization enthalpy is minimum for: [Main Jan. 08, 2020]
(A) Co (B) Fe (C) Ni (D) Mn
40. The atomic radius of Ag is closest to: [Main Jan. 07,2020]
(A) Au (B) Ni (C) Cu (D) Hg

41. Identify the element for which electronic configuration in +3 oxidation state is [Ar]3d5 :
[Main Sep. 1, 2021]
(A) Ru (B) Mn (C) Co (D) Fe
42. Potassium permanganate on heating at 513 K gives a product which is:
[Main Aug. 27, 2021]
(A) paramagnetic and colourless (B) diamagnetic and green
(C) diamagnetic and colourless (D) paramagnetic and green

APNI KAKSHA 29
(Organic Chemistry) d-BLOCK ELEMENTS
43. In the ground state of atomic Fe(Z = 26), the spin-only magnetic moment is _______ × 10−1 BM.
(Round off to the nearest integer).
[Given : √3 = 1.73, √2 = 1.41] [Main March 17, 2021 (III)]

44. The reaction of zinc with excess of aqueous alkali, evolves hydrogen gas and gives
[Main July 29, 2022]
(A) Zn(OH)2 (B) ZnO (C) [Zn(OH)4 ]2− (D) [ZnO2 ]2−

45. The total number of Mn = O bonds in Mn2 O7 is [Main July 27, 2022]
(A) 4 (B) 5 (C) 6 (D) 3
46. Dihydrogen reacts with CuO to give [Main June 28, 2022]
(A) CuH2 (B) Cu (C) Cu2 O (D) Cu(OH)2
47. Among the following, which is the strongest oxidizing agent? [Main June 25, 2022]
(A) Mn3+ (B) Fe3+ (C) Ti3+ (D) Cr 3+

48. The disproportionation of MnO2−

4 in acidic medium resulted in the formation of two manganese

compounds A and B. If the oxidation state of Mn in B is smaller than that of A, then the spin-
only magnetic moment (μ) value of B in BM is ________ . (Nearest integer)

[Main July 28, 2022 (I)]

49. The spin-only magnetic moment value of the compound with strongest oxidizing ability among
MnF4 , MnF3 and MnF2 is ________ B.M. [nearest integer] [Main July 26, 2022 (II)]

50. The spin-only magnetic moment value of M 3+ ion (in gaseous state) from the pairs
Cr 3+ /Cr 2+ , Mn3+ /Mn2, Fe3+ /Fe2+ and Co3+ /Co2+ that has negative standard electrode
potential is _________ B.M. [Nearest integer] [Main July 25, 2022 (II)]

51. The number of statement(s) correct from the following for copper (at no. 29) is/are ________ .

[Main June 27, 2022 (I)]

(A) Cu (II) complexes are always paramagnetic

(B) Cu (I) complexes are generally colourless
(C) Cu(I) is easily oxidized
(D) In Fehling solution, the active reagent has Cu (I)

52. Acidified potassium permanganate solution oxidises oxalic acid. The spin-only magnetic
moment of the manganese product formed from the above reaction is ________ . B.M. (Nearest
Integer) [Main June 27, 2022 (I)]

APNI KAKSHA 30
(Organic Chemistry) d-BLOCK ELEMENTS
EXERCISE-III
JEE-ADVANCED
1. Amongst the following identify the species with an atom in +6 oxidation state.
[JEE 2000, 3/35]
(A) MnO4
−
(B) Cr(CN)6 3−
(C) NiF6
2−
(D) CrO2 Cl2

2. Write the balanced chemical equations for developing photographic films.

3. In the standardization of Na2 S2 O3 using K 2 Cr2 O7 by iodometry, the equivalent weight of

K 2 Cr2 O7 is : [JEE 2001, 3/35]
(A) (molecular weight )/2, ( molar mass )/2
(B) (molecular weight) /6
(C) (molecular weight )/3
(D) same as molecular weight
4. Anhydrous ferric chloride is prepared by : [JEE 2002, 3/150]
(A) heating hydrated ferric chloride at a high temperature in a stream of air.
(B) heating metallic iron in a stream of dry chlorine.
(C) reaction of metallic iron with hydrochloric acid.
(D) reaction of metallic iron with nitric acid.

5. When MnO2 is fused with KOH, a coloured compound is formed. The product and its colour is:
[JEE 2003, 3/144]
(A) K 2 MnO4 , green (B) Mn2 O3 , brown
(C) Mn2 O4 , black (D) KMnO4 , purple

6. The product of oxidation of I− with MnO−

4 in alkaline medium is : [JEE 2004, 3/144]
(A) IO3
−
(B) I2 (C) IO −
(D) IO4
−

7. The pair of compounds having metals in their highest oxidation state is:[JEE 2004, 3/144]
(A) MnO2 , FeCl3 (B) [MnO4 ]− , CrO2 Cl2
(C) [Fe(CN)6]2− , [Co(CN)6 ]3− (D) [NiCl4 ]2− , [Ni(CO)4 ].
8. Which of the following pair of compounds is expected to exhibit same colour in aqueous
solution? [JEE 2005, 3/84]
(A) FeCl3 , CuCl2 (B) VOCl2 , CuCl2 (C) VOCl2 , FeCl2 (D) FeCl2 , MnCl2

9. Give equations and describe the process for the developing of black and white photographic
film. When sodium thiosulphate solution is treated with acidic solution turns milky white. Give
the half reaction of the above described process. [JEE 2005, 4/60]

APNI KAKSHA 31
(Organic Chemistry) d-BLOCK ELEMENTS
10. [JEE 2005, 4/60]

Identify (A), (B) and (C). Also explain colour difference between MCl4 and (B).

11. Match the reactions in Column I with nature of the reactions/type of the products in Column II.
[JEE 2007, 6/162]
Column I Column II
(A) O2 → O2 + O2
− 2−
(P) Redox reaction
(B) CrO4 + H →
2− +
(Q) One of the products has trigonal planar structure
(C) MnO4 + NO2 + H →
− − +
(R) Dimeric bridged tetrahedral metal ion
(D) NO3 + H2 SO4 + Fe →
− 2+
(S) Disproportionation

12. Among the following, the coloured compound is : [JEE 2008, 3/163]
(A) CuCl (B) K 3 [Cu(CN)4 ] (C) CuF2 (D) [Cu(CH3 CN)4 ]BF4

13. The oxidation number of Mn in the product of alkaline oxidative fusion of MnO2 is.
[JEE 2009, 4/160]

14. Reduction of the metal centre in aqueous permanganate ion involves: [JEE 2011, 4/180]
(A) 3 electrons in neutral medium (B) 5 electrons in neutral medium
(C) 3 electrons in alkaline medium (D) 5 electrons in acidic medium

15. The colour of light absorbed by an aqueous solution of CuSO4 is: [JEE 2012, 3/136]
(A) organge-red (B) blue-green (C) yellow (D) violet

16. Which of the following halides react(s) with AgNO3 (aq) to give a precipitate that dissolves in
Na2 S2 O3 (aq) ? [JEE 2012, 4/136]
(A) HCl (B) HF (C) HBr (D) HI

17. Consider the following list of reagents: [JEE(Advanced) 2014, 3/120]

Acidified K 2 Cr2 O7 , alkaline KMnO4 , CuSO4 , H2 O2 , Cl2 , O3 , FeCl3 , HNO3 and Na2 S2 O3 . The total
number of reagents that can oxidise aqueous iodide to iodine is

APNI KAKSHA 32
(Organic Chemistry) d-BLOCK ELEMENTS
18. The correct statement(s) about Cr 2+ and Mn3+ is (are) : [JEE(Advanced) 2015, 4/168]
[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, 4/168]

(A) H2 O2 in presence of NaOH
(B) Na2 O2 in water
(C) H2 O2 in presence of H2 SO4
(D) Na2 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]
(1) Y is diamagnetic in nature while Z is paramagnetic
(2) In aqueous acidic solution, Y undergoes disproportionation reaction to give Z and MnO2
(3) Both Y and Z are coloured and have tetrahedral shape
(4) 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]

APNI KAKSHA 33
(Organic Chemistry) d-BLOCK ELEMENTS
NCERT EXAMPLER
Multiple Choice Questions (Type-I)
1. Electronic configuration of a transition element X in +3 oxidation state is [Ar]3 d5 . What is its
atomic number?
(A) 25 (B) 26 (C) 27 (D) 24

2. The electronic configuration of Cu(II) is 3 d9 whereas that of Cu(I) is 3 d10 . Which of the
following is correct?
(A) Cu (II) is more stable
(B) Cu(II) is less stable
(C) Cu(I) and Cu (II) are equally stable
(D) Stability of Cu(I) and Cu(II) depends on nature of copper salts

3. Metallic radii of some transition elements are given below. Which of these elements will have
highest density?
Element Fe Co Ni Cu
Metallic radii/pm 126 125 125 128
(A) Fe (B) Ni (C) Co (D) Cu

4. Generally transition elements form coloured salts due to the presence of unpaired electrons.
Which of the following compounds will be coloured in solid state?
(A) Ag 2 SO4 (B) CuF2 (C) ZnF2 (D) Cu2 Cl2

5. On addition of small amount of KMnO4 to concentrated H2 SO4 , a green oily compound is

obtained which is highly explosive in nature. Identify the compound from the following.
(A) Mn2 O7 (B) MnO2 (C) MnSO4 (D) Mn2 O3

6. The magnetic nature of elements depends on the presence of unpaired electrons. Identify the
configuration of transition element, which shows highest magnetic moment.
(A) 3d7 (B) 3d5 (C) 3 d8 (D) 3d2

7. Which of the following reactions are disproportionation reactions?

(a) 2Cu+ → Cu2+ + Cu (b) 3MnO2− + −
4 + 4H → 2MnO4 + MnO2 + 2H2 O
(c) 2KMnO4 → K 2 MnO4 + MnO2 + O2 (d) 2MnO− 4 + 3Mn
2+
+ 2H2 O → 5MnO2 + 4H +
(A) a, b (B) a, b, c (C) b, c, d (D) a, d

8. When KMnO4 solution is added to oxalic acid solution, the decolourisation is slow in the
beginning but becomes instantaneous after some time because
(A) CO2 is formed as the product. (B) Reaction is exothermic.
(C) MnO4 catalyses the reaction.
−
(D) Mn2+ acts as autocatalyst.

APNI KAKSHA 34
(Organic Chemistry) d-BLOCK ELEMENTS
9. KMnO4 acts as an oxidising agent in acidic medium. The number of moles of KMnO4 that will be
needed to react with one mole of sulphide ions in acidic solution is
2 3 4 1
(A) 5 (B) 5 (C) 5 (D) 5

10. Which of the following is amphoteric oxide?

Mn2 O7 , CrO3 , Cr2 O3 , CrO, V2 O5 , V2 O4
(A) V2 O5 , Cr2 O3 (B) Mn2 O7 , CrO3 (C) CrO, V2 O5 (D) V2 O5 , V2 O4

11. Interstitial compounds are formed when small atoms are trapped inside the crystal lattice of
metals. Which of the following is not the characteristic property of interstitial compounds?
(A) They have high melting points in comparison to pure metals.
(B) They are very hard.
(C) They retain metallic conductivity.
(D) They are chemically very reactive.

12. The magnetic moment is associated with its spin angular momentum and orbital angular
momentum. Spin only magnetic moment value of Cr 3+ ion is__________.
(A) 2.87 B.M. (B) 3.87 B.M. (C) 3.47 B.M. (D) 3.57 B.M.

13. KMnO4 acts as an oxidising agent in alkaline medium. When alkaline KMnO4 is treated with KI,
iodide ion is oxidised to__________.
(A) I2 (B) IO− (C) IO−
3 (D) IO−4

14. Which of the following statements is not correct?

(A) Copper liberates hydrogen from acids.
(B) In its higher oxidation states, manganese forms stable compounds with oxygen and
fluorine.
(C) Mn3+ and Co3+ are oxidising agents in aqueous solution.
(D) Ti2+ and Cr 2+ are reducing agents in aqueous solution.

15. When acidified K 2 Cr2 O7 solution is added to Sn2+ salts then Sn2+ changes to
(A) Sn (B) Sn3+ (C) Sn4+ (D) Sn+

16. Highest oxidation state of manganese in fluoride is +4(MnF4 ) but highest oxidation state in
oxides is +7(Mn2 O7 ) because
(A) fluorine is more electronegative than oxygen.
(B) fluorine does not possess d-orbitals.
(C) fluorine stabilises lower oxidation state.
(D) in covalent compounds fluorine can form single bond only while oxygen forms double
bond.

APNI KAKSHA 35
(Organic Chemistry) d-BLOCK ELEMENTS
17. Why is HCl not used to make the medium acidic in oxidation reactions of KMnO4 in acidic
medium?
(A) Both HCl and KMnO4 act as oxidising agents.
(B) KMnO4 oxidises HCl into Cl2 which is also an oxidising agent.
(C) KMnO4 is a weaker oxidising agent than HCl.
(D) KMnO4 acts as a reducing agent in the presence of HCl.

II. Multiple Choice Questions (Type-II)

Note: In the following questions two or more options may be correct.

18. Transition elements show magnetic moment due to spin and orbital motion of electrons. Which
of the following metallic ions have almost same spin only magnetic moment?
(A) Co2+ (B) Cr 2+ (C) Mn2+ (D) Cr 3+

19. In the form of dichromate, Cr(VI) is a strong oxidising agent in acidic medium but Mo(VI) in
MoO3 and W(VI) in WO3 are not because
(A) Cr(VI) is more stable than Mo(VI) and W(VI).
(B) Mo(VI) and W(VI) are more stable than Cr(VI).
(C) Higher oxidation states of heavier members of group-6 of transition series are more stable.
(D) Lower oxidation states of heavier members of group-6 of transition series are more stable.

20. Which of the following ions show higher spin only magnetic moment value?
(A) Ti3+ (B) Mn2+ (C) Fe3+ (D) Co3+

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

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

(A) CrO3 (B) MoO3 (C) WO3 (D) CrO2−
4

III. Short Answer Type

23. Why does copper not replace hydrogen from acids?

24. Why E 0 values for Mn, Ni and Zn are more negative than expected?

25. Why first ionisation enthalpy of Cr is lower than that of Zn ?

26. Transition elements show high melting points. Why?

27. When Cu2+ ion is treated with KI, a white precipitate is formed. Explain the reaction with the
help of chemical equation.
APNI KAKSHA 36
(Organic Chemistry) d-BLOCK ELEMENTS
28. Out of Cu2 Cl2 and CuCl2 , which is more stable and why?

29. When a brown compound of manganese (A) is treated with HCl it gives a gas (B). The gas taken
in excess, reacts with NH3 to give an explosive compound (C). Identify compounds A, B and C.

30. Although fluorine is more electronegative than oxygen, but the ability of oxygen to stabilise
higher oxidation states exceeds that of fluorine. Why?

31. Although Cr 3+ and Co2+ ions have same number of unpaired electrons but the magnetic
moment of Cr 3+ is 3.87 B.M. and that of Co2+ is 4.87 B.M. Why?

32. Explain why does colour of KMnO4 disappear when oxalic acid is added to its solution in acidic
medium.

33. When orange solution containing Cr2 O2−

7 ion is treated with an alkali, a yellow solution is
formed and when H ions are added to yellow solution, an orange solution is obtained. Explain
+

why does this happen?

34. A solution of KMnO4 on reduction yields either a colourless solution or a brown precipitate or a
green solution depending on pH of the solution. What different stages of the reduction do these
represent and how are they carried out?

35. E 0 of Cu is +0.34 V while that of Zn is −0.76 V. Explain.

36. The halides of transition elements become more covalent with increasing oxidation state of the
metal. Why?

37. While filling up of electrons in the atomic orbitals, the 4 s orbital is filled before the 3 d orbital
but reverse happens during the ionisation of the atom. Explain why?

38. Reactivity of transition elements decreases almost regularly from Sc to Cu. Explain.

IV. Matching Type

Note: Match the items of Column I and Column II in the following questions.

39. Match the catalysts given in Column I with the processes given in Column II.
Column I (Catalyst) Column II (Process)
(A) Ni in the presence of hydrogen (i) Zieglar Natta catalyst
(B) Cu2 Cl2 (ii) Contact process
(C) V2 O5 (iii) Vegetable oil to ghee
(D) Finely divided iron (iv) Sandmeyer reaction
(E) TiCl4 + Al(CH3 )3 (v) Haber's Process
(F) Decomposition of KClO3
APNI KAKSHA 37
(Organic Chemistry) d-BLOCK ELEMENTS
40. Match the properties given in Column I with the metals given in Column II.
Column I (Property) Column II (Metal)
(A) An element which can show +8 oxidation state (i) Mn
(B) 3 d series element that can show upto +7 oxidation state (ii) Cr
(C) 3 d series element with highest melting point (iii) Os
(iv) Fe

41. Match the solutions given in Column I and the colours given in Column II.
Column I (Aqueous solution of salt) Column II (Colour)
(A) FeSO4 ⋅ 7H2 O (i) Green
(B) NiCl2 ⋅ 4H2 O (ii) Light pink
(C) MnCl2 ⋅ 4H2 O (iii) Blue
(D) CoCl2 ⋅ 6H2 O (iv) Pale green
(E) Cu2 Cl2 (v) Pink
(vi) Colourless

42. Match the properties given in Column I with the metals given in Column II.
Column I (Property) Column II (Metal)
(A) Element with highest second ionisation enthalpy (i) Co
(B) Element with highest third ionisation enthalpy (ii) Cr
(C) M in M(CO)6 is (iii) Cu
(D) Element with highest heat of atomization (iv) Zn
(v) Ni
V. Assertion and Reason Type
Note: In the following questions a statement of assertion followed by a statement of reason is
given. Choose the correct answer out of the following choices.
(A) Both assertion and reason are true, and reason is the correct explanation of the assertion.
(B) Both assertion and reason are true but reason is not the correct explanation of assertion.
(C) Assertion is not true but reason is true.
(D) Both assertion and reason are false.

43. Assertion: Cu2+ iodide is not known.

Reason: Cu2+ oxidises I − to iodine.

44. Assertion: Cu cannot liberate hydrogen from acids.

Reason: Because it has positive electrode potential.

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

Reason: Osmium is a 5d-block element.

APNI KAKSHA 38
(Organic Chemistry) d-BLOCK ELEMENTS
46. Identify A to E and also explain the reactions involved.

47. When a chromite ore (A) is fused with sodium carbonate in free excess of air and the product is
dissolved in water, a yellow solution of compound (B) is obtained. After treatment of this
yellow solution with sulphuric acid, compound (C) can be crystallised from the solution. When
compound (C) is treated with KCl, orange crystals of compound (D) crystallise out. Identify A to
D and also explain the reactions.
48. When an oxide of manganese (A) is fused with KOH in the presence of an oxidising agent and
dissolved in water, it gives a dark green solution of compound (B). Compound (B)
disproportionates in neutral or acidic solution to give purple compound (C). An alkaline
solution of compound (C) oxidises potassium iodide solution to a compound (D) and
compound (A) is also formed. Identify compounds A to D and also explain the reactions
involved.

49. (I) Answer the following questions :

(A) Which element of the first transition series has highest second ionisation enthalpy?
(B) Which element of the first transition series has highest third ionisation enthalpy?
(C) Which element of the first transition series has lowest enthalpy of atomisation?
(II) Identify the metal and justify your answer.
(A) Carbonyl M(CO)5
(B) MO3 F

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

51. (a) Transition metals can act as catalysts because these can change their oxidation state. How
does Fe(III) catalyse the reaction between iodide and persulphate ions?
(b) Mention any three processes where transition metals act as catalysts.
52. A violet compound of manganese (A) decomposes on heating to liberate oxygen and
compounds (B) and (C) of manganese are formed. Compound (C) reacts with KOH in the
presence of potassium nitrate to give compound (B). On heating compound (C) with conc.
H2 SO4 and NaCl, chlorine gas is liberated and a compound (D) of manganese along with other
products is formed. Identify compounds A to D and also explain the reactions involved.

APNI KAKSHA 39
(Organic Chemistry) d-BLOCK ELEMENTS
ANSWER KEY
Do yourself – 1
Question 1 2 3 4 5
Answer B,C,D A,B A A,B B
Do yourself – 2
Question 1 2 3 4 5
Answer A A B D A,B
EXERCISE-I
Q.1 B Q.2 A Q.3 B Q.4 A,B,C Q.5 A,B Q.6 B Q.7 A,B,C,D
Q.8 A Q.9 B Q.10 A Q.11 A,B, D Q.12 A,B,C Q.13 B,C Q.14 B
Q.15 B Q.16 A Q.17 B Q.18 D Q.19 B Q.20 C Q.21 A,B,C
Q.22 A,B,C Q.23 A Q.24 A,B,C Q.25 B Q.26 A Q.27 A Q.28 B,C
Q.29 D Q.30 A Q.31 B Q.32 A,C Q.33 D Q.34 A Q.35 A,B
Q.36 C Q.37 D Q.38 A,B,C,D
Q.39 C Q.40 B Q.41 C Q.42 A Q.43 A,B Q.44 C Q.45 D
Q.46 A Q.47 A Q.48 A,B,C Q.49 A Q.50 A,B Q.51 B Q.52 B,C
Q.53 C Q.54 B Q.55 A Q.56 B Q.57 D Q.58 A Q.59 B
Q.60 B Q.61 A Q.62 B Q.63 C Q.64 C Q.65 B Q.66 A
Q.67 A Q.68 C

EXERCISE-II (JEE-Main)

1. (A) 2. (A) 3. (A) 4. (A) 5. (C) 6. (A) 7. (A)

8. (D) 9. (B) 10. (D) 11. (C) 12. (C) 13. (D) 14. (A)

15. (D) 16. (B) 17. (B) 18. (A) 19. (A) 20. (B) 21. (A)

22. (D) 23. (D) 24. (D) 25. (A) 26. (D) 27. (D) 28. (B)

29. (C) 30. (D) 31. (A) 32. (C) 33. (A) 34. (B) 35. (B)

36. (A) 37. (C) 38. (C) 39. (B) 40. (A) 41. (D) 42. (D)

43. (49) 44. (C) 45. (C) 46. (B) 47. (A) 48. (4) 49. (5)

50. (4) 51. (3) 52. (6)

APNI KAKSHA 40
(Organic Chemistry) d-BLOCK ELEMENTS
JEE-MAIN
SOLUTION

35. (2) I.E. increases on moving left to right in a period.

∴ Ti < Mn < Ni < Zn

513 K
36. (a) 2KMnO4 ⟶ K 2 MnO4 + MnO2 + O2
(X) (Y) gas
MnO2 + 4NaCl + 4H2 SO4 → MnCl2 + 4NaHSO4 + Cl2 + 2H2 O
Conc. (Z)
Pungent gas
37. (c)
(A) V2 O5 → Preparation of H2 SO4 in contact process
(B) TiCl4 + Al(Me)3 → Polyethylene (Ziegler-Natta catalyst)
(C) PdCl2 → Ethanol (Wacker's process)
(D) Iron oxide → NH3 in (Haber's process)

38. (C)

Manganate ion is paramagnetic while permanganate ion is diamagnetic.

39. (b) 20 Fe = [Ar]3d6 4s2 . Third ionisation results into stable d5 configuration.

40. (a) Atomic size of elements of 4d and 5d transition series are nearly same due to lanthanide
contraction.

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(Organic Chemistry) d-BLOCK ELEMENTS
41. (d) Fe3+ = [Ar]3d5

42. (d) Potassium permanganate on heating at 513 K gives potassium manganate (K 2 MnO4 ) and its
colour is green.

2KMnO4 ⎯⎯⎯
513 K
→ K 2 MnO4 + MnO2 + O2
Green Black

In K 2 MnO4 , manganese oxidation state is +6 and hence, it as one unpaired electron and
paramagnetic.

43. ˙ (Z = 26) ⇒ [Ar]3d6 4s 2

Fe

Number of unpaired electrons = 4

44. (c) Zinc dissolves in excess of aqueous alkali.

Zn(s) + 2OH − (aq) + 2H2 O(l) → [Zn(OH)4 ]2− (aq) + H2 ( g)
Tetrahydroxozincate (II) ion

2 is anhydrous form of [Zn(OH)4 ]

ZnO2− 2−

So in aqueous medium best answer of this question is [Zn(OH)4 ]2 .

45. (c) In manganese heptoxide, there are 6, Mn = 0 bonds.

46. (b) Copper get reduced and hydrogen get oxidised

CuO + H2 → Cu + H2 O (under hot conditions)

47. (a) Strongest oxidising agent have highest reduction potential value.
∘
EMn 3+ /Mn2+ = 1.51 V (highest)

H+
48. MnO2− −
4 ⟶ MnO2 + MnO2
No. of unpaired e− (n) = 3

∴ μ = √n(n + 2) = √15 = 3.877 B.M.

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(Organic Chemistry) d-BLOCK ELEMENTS
49. MnF4 ⇒ +4 state ⇒ [Ar]3 d3

MnF3 ⇒ +3 state ⇒ [Ar]3 d4

(Strongest O.A)

MnF2 ⇒ +2 state ⇒ [Ar]3 d5

For n = 4,
∴ μ5 = √4(4 + 2) = √24 = 4.89 = 5
50. In case of conversion of Cr 3+ → Cr 2+ the e− is added to eg orbital, hence electrode potential is
negative.
∘
ECr+3 /Cr+2 = −0.41 V

[Cr +3 ] = 4 s0 3 d3
μ = √n(n + 2) B.M = √15 B.M 4 B.M

51. A, B, C are correct and D is incorrect because Fehling solution has Cu (II).
52. 2KMnO4 + 5H2 C2 O4 + 3H2 SO4 →

K 2 SO4 + 2MnSO4 + 10CO2 + 8H2 O.

Mn2+ has 5 unpaired electrons, therefore, the magnetic moment = √5(5 + 2) = √35BM.

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(Organic Chemistry) d-BLOCK ELEMENTS
EXERCISE-III (JEE-ADVANCED)
1. (D)
2. C6 H4 (OH)2 + 2AgBr ⟶ 2Ag + C6 H4 O2 + 2HBr.
AgBr + 2Na2 S2 O3 ⟶ Na3 [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 + 2Na2 S2 O3 ⟶ Na3 [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 .

Oxygen atoms bonded to chromium through only single bonds = 4

APNI KAKSHA 44
(Organic Chemistry) d-BLOCK ELEMENTS
NCERT EXAMPLER
I. Multiple Choice Questions (Type-I)
1. (B) 2. (A) 3. (D) 4. (B) 5. (A) 6. (B) 7. (A)
8. (D) 9. (A) 10. (A) 11. (D) 12. (B) 13. (C) 14. (A)
15. (C) 16. (D) 17. (B)
II. Multiple Choice Questions (Type-II)
18. (A),(D) 19. (B), (C) 20. (B), (C) 21. (A), (B)
22. (B), (C)
III. Short Answer Type
23. Cu shows positive E ⊖ value.
24. Hint : Negative E Θ values for Mn2+ and Zn2+ are related to stabilities of half filled and fully filled
configuration respectively. But for Ni2+ , E Θ value is related to the highest negative enthalpy of
hydration.
25. Ionisation enthalpy of Cr is lower due to stability of d5 and the value for Zn is higher because
its electron comes out from 4 s orbital.
26. The high melting points of transition metals are attributed to the involvement of greater
number of electrons in the interatomic metallic bonding from (n-1) d-orbitals in addition to ns
electrons
27. Hint : Cu2+ gets reduced to Cu+
2Cu2+ + 4Γ → Cu2 I2 + I2
(white precipitate)
28. Hint : CuCl2 is more stable than Cu2 Cl2 . The stability of Cu2+ (aq.) rather than Cu+ (aq.) is due to
the much more negative .hydH Θ of Cu2+ (aq.) than Cu + (aq.).
29. A = MnO2 B = Cl2 C = NCl3
MnO2 + 4HCl → MnCl2 + Cl2 + 2H2 O
(A) (B)
NH3 + 3Cl2 → NCl3 + 3HCl
(excess) (C)
30. Hint: It is due to the ability of oxygen to form multiple bonds to metals.
31. Hint: Due to symmetrical electronic configuration there is no orbital contribution in Cr 3+ ion.
However appreciable orbital contribution takes place in Co2+ ion.
32. KMnO4 acts as oxidising agent. It oxidises oxalic acid to CO2 and itself changes to Mn2+ ion
which is colourless.
5C2 O2− −
4 + 2MnO4 + 16H → 2Mn
+ 2+
+ 8H2 O + 10CO2
(Coloured) (Colourless)
33. Cr2 O72−

Dichromate Chromate
(Orange) (Yellow)
34. Oxidising behaviour of KMnO4 depends on pH of the solution. In acidic medium (pH < 7)
MnO− + −
4 + 8H + 5e → Mn
2+
+ 4H2 O
(Colourless)
In alkaline medium (pH > 7)
MnO− 4 + e → MnO4
2−

APNI KAKSHA 45
(Organic Chemistry) d-BLOCK ELEMENTS
(Green)
In neutral medium (pH = 7)
MnO2− −
4 + 2H2 O + 3e → MnO2 + 4OH
−

(Brown precipitate)
35. Hint: High ionisation enthalpy to transform Cu(s) to Cu2+ (aq) is not balanced by its hydration
enthalpy. However, in case of Zn after removal of electrons from 4 s-orbital, stable 3 d10
configuration is acquired.
36. As the oxidation state increases, size of the ion of transition element decreases. As per Fajan's
rule, as the size of metal ion decreases, covalent character of the bond formed increases.
37. n + l rule : For 3 d = n + l = 54 s = n + l = 4
So electron will enter in 4 s orbital.
Ionisation enthalpy is responsible for the ionisation of atom. 4 s electrons are loosely held by
the nucleus. So electrons are removed from 4 s orbital prior to 3 d.
38. Hint : It is due to regular increase in ionisation enthalpy.
IV. Matching Type
39. (A) → (iii) ; (B) → (iv) ; (C) → (ii) ; (D) → (v) ; (E) → (i)
40. (A) → (iii) ; (B) → (i) ; (C) → (ii)
41. (A) → (iv) ; (B) → (i) ; (C) → (ii) ; (D) → (v) ; (E) → (vi)
42. (A) → (iii) ; (B) → (iv) ; (C) → (ii) ; (D) → (i)
V. Assertion and Reason Type
43. (A) 44. (A) 45. (B)
VI. Long Answer Type
46. A = Cu B = Cu(NO3 )2 C = [Cu(NH3 )4 ] D = CO2
E = CaCO3 F= Cu2 [Fe(CN)6 ] G = Ca(HCO3 )2
CuCO3 → CuO + CO2
CuO + CuS → Cu + SO2
(A)
Cu + 4HNO3 (Conc) → Cu(NO3 )2 + 2NO + 2H2 O
(B)
2+ 3
Cu + NH → [Cu(NH3 )4 ]
(B) (C)
Ca(OH)2 + CO2 → CaCO3 + H2 O
(D) (E)
CaCO3 + H2 O + CO2 → Ca(HCO3 )2
47. A = FeCr2 O4 B = Na2 CrO4 C = Na2 Cr2 O7 ⋅ 2H2 O D = K 2 Cr2 O7
4FeCr2 O4 + 8Na2 CO3 + 7O2 → 8Na2 CrO4 + 2Fe2 O3 + 8CO2
(A) (B)
2NaCrO4 + 2H → Na2 Cr2 O7 + 2Na+ + H2 O
+

Na2 Cr2 O7 + 2KCl → K 2 Cr2 O7 + 2NaCl

(C) (D)
48. A = MnO2 (B) K 2 MnO4 (C) KMnO4 (D) KIO3
2MnO2 + 4KOH + O2 → 2 K 2 MnO4 + 2H2 O
(A) (B)
APNI KAKSHA 46
(Organic Chemistry) d-BLOCK ELEMENTS
3MnO4 2− + 4H + → 2MnO− 4 + MnO2 + 2H2 O
(C)
−
2MnO4 + H2 O + KI → 2MnO2 + 2OH − + KIO3
(A) (D)
49. (a) (A) Cu, because the electronic configuration of Cu is 3 d10 4 s1 . So second electron needs to
be removed from completely filled d-orbital.
(B) Zn [Hint : As above]
(C) Zn [Hint : No unpaired electron for metallic bonding]
(b) (A) Fe(CO)5 [ Hint : EAN rule ]
(B) MnO3 F [Hint : Mn shows +7 oxidation state; d-electrons are not involved in bonding.]
50. Interstitial compounds.
Characteristic properties :
(A) High melting points, higher than those of pure metals.
(B) Very hard.
(C) Retain metallic conductivity.
(D) Chemically inert.
51. (a) Reaction between iodide and persulphate ions is :
Fe(III)
2I − + S2 O8 2− ⟶ I2 + 2SO4 2−
Role of Fe (III) ions :
2Fe3+ + 2I − → 2Fe2+ + I2
2Fe2+ + S2 O8 2− → 2Fe3+ + 2SO4 2−
(b) (A) Vanadium (V) oxide in contact process for oxidation of SO2 to SO3 .
(B) Finely divided iron in Haber's process in conversion of N2 and H2 to NH3 .
(C) MnO2 in preparation of oxygen from KClO3 .
52. A = KMnO4 B = K 2 MnO4 C = MnO2 D = MnCl2
Δ
KMnO4 ⟶ K 2 MnO4 + MnO2 + O2
(A) (B) (C)
MnO2 + KOH + O2 → 2 K 2 MnO4 + 2H2 O
MnO2 + 4NaCl + 4H2 SO4 → MnCl2 + 2NaHSO4 + 2H2 O + Cl2
(D)

APNI KAKSHA 47