D- & F-BLOCK ELEMENTS

D-BLOCK ELEMENTS (CLASS ASSIGNMENT)

PROPERTIES OF D-BLOCK ELEMENTS

With the exceptions of Zn, Cd, Hg and Mn, they have one or more typical metallic
structures at normal temperatures.

Melting Point

The transition metals (with the exception of Zn, Cd and Hg) are very hard and have low volatility.
Their melting and boiling points are high.
In any row the melting points of these metals rise to a maximum at d5 except for anomalous values
of Mn and Tc and fall regularly as the atomic number increases.

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Atomic Radii

OXIDATION STATE
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+3 +2 +2 +2 +2 +2 +2 +2 +1 +2
+3 +3 +3 +3 +3 +3 +3 +2
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5
+6 +6 +6
+7

 The maximum oxidation states of reasonable stability is the sum of the s and d electrons
upto manganese (TiO2, VO2+, CrO42–, MnO4–)

 In the p–block the lower oxidation states are favoured by the heavier members (due to inert
pair effect), the opposite is true in the groups of d-block. For example, 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.

 Low oxidation states are found when  acid ligands are present like, in Ni(CO)4 and
Fe(CO)5, the oxidation state of nickel and iron is zero.

Standard Electrode Potential (M2+/M):

Element (M) oH(M) 1H1⊝ 1H2⊝ hydH⊝ (M2+) E⊝ /V

Ti 469 656 1309 – 1866 – 1.63
V 515 650 1414 – 1895 – 1.18
Cr 398 653 1592 – 1925 – 0.9
Mn 279 717 1509 – 1862 – 1.18
Fe 418 762 1561 – 1998 – 0.44
Co 427 758 1644 – 2079 – 0.28
Ni 431 736 1752 – 2121 – 0.25
Cu 339 745 1958 – 2121 0.34
Zn 130 906 1734 – 2059 – 0.76

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FORMATION OF COLOURED COMPOUNDS:

Fig.: Colours of some of the first row transition metal ions in aqueous solutions. From left to
right: V4+, V3+, Mn2+, Fe3+,Co2+, Ni2+ and Cu2+.

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. They are usually non stoichiometric and are
neither typically ionic nor covalent, for example, TiC, Mn4N, Fe3H, VH0.56 and TiH1.7, etc.
The formulas quoted do not, of course, correspond to any normal oxidation state of the
metal. Because of the nature of their composition, these compounds are referred to as
interstitial compounds. 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.

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Oxides of 3d Metals:

Questions: In first transition series, the melting point of Mn is low because

(A) Due to d10 configuration, metallic bonds are strong

(B) Due to d7 configuration, metallic bonds are weak

(C) Due to d5 configuration, metallic bonds are weak

(D) None of these

Ans. C

Questions: The atomic radii of the elements are almost same of which series.

(A) Fe – Co – Ni (B) Na – K – Rb (C) F – Cl – Br (D) Li – Be – B

Ans. A

OXIDES & OXOANIONS OF METALS

As the oxidation number of a metal increases, ionic character decreases. In the case of Mn,
Mn2O7 is a covalent green oil. Even CrO3 and V2O5 have low melting points. In these higher
oxides, the acidic character is predoinant.

Thus, Mn2O7 gives HMnO4 and CrO3 gives H2CrO4 and H2Cr2O7. V2O5 is, however,
amphoteric though mainly acidic and it gives VO43– as well as VO2+ salts. In vanadium there
is gradual change from the basic V2O3 to less basic V2O4 and to amphoteric V2O5. V2O4
dissolves in acids to give VO2+ salts. Similarly, V2O5 reacts with alkalies as well as acids to
give VO43– and VO4+ respectively. The well characterised CrO is basic but Cr2O3 is
amphoteric.

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POTASSIUM DICHROMATE
K2Cr2O7:

O O
O
Potassium Cr Cr
dichromate +  O K+
KO
K2Cr2O7 O O

Prepared from

Chromite ore
FeCr2O4

Step-1: Conversion of chromite ore into sodium chromate.

4FeCr2O4 + 16NaOH + 7O2 ⟶ 8Na2CrO4 + 2Fe2O3 + 8H2O

Chromite ore (Air)

or 4FeCr2O4 + 8Na2CO3 + 7O2 ⟶ 8Na2CrO4 + 2Fe2O3 + 8CO2

Step-2: Conversion of sodium chromate into sodium dichromate

on cooling
2Na 2CrO4  H 2SO4  Na2 Cr2O7  Na2 SO4  H 2O 
Crysallizes out as
 Na 2SO4 .10H 2O

Step-3: Conversion of sodium dichromate into potassium dichromate

Na2Cr2O7 + 2KCl  K2Cr2O7 + 2NaCl

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Colour and Melting Point:

Orange red Crystalline solid Melting point  670 K

Solubility:

Moderately soluble in cold water but readily soluble in hot water

Action of heat:

It decomposes on heating to form potassium chromate, chromic oxide and oxygen.

4K2Cr2O7  4K2CrO4 + 2Cr2O3 + 3O2

Potassium Chromic
Chromate oxide

Action with alkalis:

+ 2KOH

K2Cr 2O7 Potassium chromate

Orange colour Yellow colour

2K2CrO4 + H2SO4  K2Cr2O7 + K2SO4 + H2O

(Yellow) (Orange)

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Properties of Potassium Dichromate:

CrO42– and Cr2O72– are inter convertible in aqueous solution depend upon PH value

2–
Low PH 2–
CrO 4 Cr2O7
High PH

Weak acid
Alkaline/
carbonate
solution

Oxidizing Character:

In acidic solution, K2Cr2O7 furnishes nascent Oxygen [O]

K2Cr2O7 + 4H2SO4 ⟶ Cr2(SO4)3 + K2SO4 + 4H2O + 3 [O]

Cr2O72– + 14H+ + 6e– ⟶ 2Cr3+ + 7H2O (E0 = 1.33 V)

+6 +3

Oxidizing Agent


K 2Cr2 O7 /H
1. Alcohol (CH3CH 2OH)   AceticAcid  CH 3COOH 

2. K2Cr2O7 + 4H2SO4 + 3H2S  3S + Cr2(SO4)3 + K2SO4 + 7H2O

3. K2Cr2O7 + 14HCl ⟶ 2KCl + 2CrCl3 + 3Cl2 + 7H2O

4. K2Cr2O7 + 7H2SO4 + 6KI  3I2 + Cr2(SO4)3 + 4K2SO4 + 7H2O

5. K2Cr2O7 + 14 HCl + 3SnCl2  3SnCl4 + 2KCl + 2CrCl3 + 7H2O

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STRUCTURE OF CHROMATE AND DICHROMATE IONS

Tetrahedral Two tetrahedra sharing one corner

heat
Question: In the given reaction X is 4K 2Cr2O7   4K 2 CrO 4  3O 2  X

(A) CrO3 (B) Cr2O7 (C) Cr2O3 (D) CrO5

Question: Acidified potassium dichromate is treated with hydrogen sulphide. In the reaction,
the oxidation number of chromium

(A) Increases from + 3 to + 6 (B) Decreases from + 6 to + 3

(C) Remains unchanged (D) Decreases from + 6 to + 2

Question: Number of moles of K2Cr2O7 reduced by one mole of Sn2+ ion is

(A) 1/3 (B) 3 (C) 16 (D) 6

POTASSIUM PERMGANATE (KMnO4)

Potassium KMnO4
permanganate

Prepared from

Pyrolusite (MnO2)

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Preparation of Potassium permanganate (KMnO4)

1. Conversion of pyrolusite ore to potassium manganate

2MnO2 + 4KOH + O2  2K2MnO4 + 2H2O

Dark green

Disproportion in neutral or acidic medium

3 +4 →2 + +2

2. Commercially it is prepared by alkaline oxidative fusion of MnO2 followed by electrolytic

oxidation of manganate (VI)

Fused with KOH, oxidised With air or KNO3

MnO 2   MnO 42
Manganate ion

Electrolytic oxidation in Alkaline solution

MnO 24   MnO 4
Manganate Permanganate ion

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

permanganate.

2Mn2+ + 5S2O82– + 8H2O ⟶ 2MnO4– + 10SO42– + 16H+

Properties of Potassium permanganate (KMnO4)

Colour and Melting point

Dark violet crystalline solid Melting point  523 K

SOLUBILITY

Fairly soluble in water giving a purple solution 6.4 g/ 100 g

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It is isostructural of KClO4

Action of Heat

When heated strongly to 513 K it decomposes to given oxygen

2KMnO4  K2MnO4 + MnO2 + O2

On heating with alkalies potassium permanganate changes into potassium manganate and
oxygen gas is evolved

4KMnO4 + 4KOH  4K2MnO4 + 2H2O + O2

OXIDISING CHARACTER

Powerful Oxidising Agent

Acidic Medium

2KMnO4 + 3H2SO4 ⟶ K2 SO4 + 2MnSO4 + 3H2O + 5[O]

Basic Medium

2KMnO4 + 2KOH ⟶ 2K2 MnO4 + H2O + [O]

Neutral Medium

2KMnO4 + H2 O ⟶ 2MnO2 + 2KOH + 3[O]

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MnO4– + e–  MnO42– (E0 = + 0.56 V)

MnO4– + 4H+ + 3e–  MnO2 + 2H2O (E0 = + 1.69 V)
MnO4– + 8H+ + 5e–  Mn2+ + 4H2O (E0 = + 1.52 V)

1. In acid solutions:

(a) Iodine is liberated from potassium iodide :

10 I– + 2MnO4– + 16H+  2Mn2+ + 8H2O + 5I2

(b) Fe2+ ion (green) is converted to Fe3+ (yellow):

5Fe2+ + MnO4– + 8H+  Mn2+ + 4H2O + 5Fe3+

(c) Oxalate ion or oxalic acid is oxidised at 333 K:

5C2O42– + 2MnO4– + 16H+  2Mn2+ + 8H2O + 10CO2

(d) Hydrogen sulphide is oxidised, sulphur being precipitated:

H2S  2H+ + S2–

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

(e) Sulphurous acid or sulphite is oxidised to a sulphate or sulphuric acid:

5SO32– + 2MnO4– + 6H+  2Mn2+ + 3H2O + 5SO42–

(f) Nitrite is oxidised to nitrate:

5NO2– + 2MnO4– + 6H+ 2Mn2+ + 5NO3– + 3H2O

2. In neutral or faintly alkaline solutions:

(a) A notable reaction is the oxidation of iodide to iodate:

2 MnO4– + H2O + I–  2MnO2 + 2OH– + IO3–

(b) Thiosulphate is oxidised almost quantitatively to sulphate:

8 MnO4– + 3S2O32– + H2O  8MnO2 + 6SO42– + 2OH–

(c) Manganous salt is oxidised to MnO2; the presence of zinc sulphate or zinc oxide
catalyses the oxidation:

2 MnO4– + 3Mn2+ + 2H2O  5MnO2 + 4H+

Note: Permanganate titrations in presence of hydrochloric acid are unsatisfactory since

hydrochloric acid is oxidised to chlorine.

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Question: n-factor of KMnO4 in neutral medium is

(A) 6 (B) 5 (C) 4 (D) 3

Question: Potassium permanganate acts as an oxidant in neutral, alkaline as well as acidic

media. The final products obtained from it in the three conditions are, respectively

(A) MnO2, MnO42–, Mn2+ (B) MnO42–, Mn3+, Mn2+

(C) MnO2, MnO22–, Mn3+ (D) MnO, MnO4, Mn2+

Question: The number of moles of KMnO4 that will be needed to react with one mole of
sulphite ion in acidic solution is

(A) 2/5 (B) 3/5 (C) 4/5 (D) 1

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F-BLOCK ELEMENTS (CLASS ASSIGNMENT)

(i) Lathanides  Silvery white metals

58 – – 71

(ii) Actinodes  Radioactive material

90 – – 103

LATHANIDES

GENERAL ELECTRONIC CONFIGURATION

(n – 2) f1 – 14 (n –1) d0 – 1ns2

How to Learn the Elements

La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

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Atomic Number Elements Symbol 4f 5d 6s

57 Lanthanum La 0 1 2

58 Cerium Ce 1 1 2

59 Praseodymium Pr 3 0 2

60 Neodymium Nd 4 0 2

61 Promethium Pm 5 0 2

62 Samarium Sm 6 0 2

63 Europium Eu 7 0 2

64 Gadolinium Gd 7 1 2

65 Terbium Tb 9 0 2

66 Dysprosium Dy 10 0 2

67 Holmium Ho 11 0 2

68 Erbium Er 12 0 2

69 Thulium Tm 13 0 2

70 Ytterbium Yb 14 0 2

71 Lutetium Lu 14 1 2

GENERAL CHARACTERISTICS

1. Silvery White soft metals

2. Tarnish rapidly in air

3. Hardness  Atomic No.

4. Good conductors of heat and electricity.

5. Ln+3 – Mostly Coloured (Solid and liquid Both)

Except La+3 & Lu+3

6. Paramagnetic except f0(La3+ and Ce4+) and f14 (Yb+2 and Lu+3)

7. Alloy steels- mischmetall which consists of a lanthanoid metal (~ 95%) and iron (~ 5%) and
traces of S, C, Ca and Al.

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8. Mischmetall is used in Mg-based alloy to produce bullets, shell and lighter flint.

9. Catalysts in petroleum cracking.

10. Some individual Ln oxides are used as phosphors in television screens and similar
fluorescing surfaces.

ATOMIC AND IONIC SIZE

1. Decrease along the period (Lanthanoid contraction)

2. The cumulative effect of the contraction of the lanthanoid series, known as lanthanoid
contraction, causes the radii of the members of the third transition series to be very similar
to those of the corresponding members of the second series.

OXIDATION STATES

+2 +3 +4
Eu+2 Most Common Ce+4, Pr+4, Nd+4,
Yb+2 Tb+4, Dy+4
(Only oxides)
1. Ln(II) and Ln(III) compounds are predominant
2. Formation of CeIV is favoured by its noble gas configuration
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3. Strong oxidant reverting to the common +3 state

4. E0 value for Ce4+/ Ce3+ is + 1.74 V which suggests that it can oxidise water
5. Reaction rate is very slow and hence Ce(IV) is a good analytical reagent.
6. Behaviour of samarium is very much like europium, exhibiting both +2 and +3 oxidation
states.

CHEMICAL REACTIONS

Earlier members of the series are quite reactive similar to calcium but, with increasing
atomic number, they behave more like aluminium.

Values for E0 for the half-reaction:

Ln3+(aq) + 3e–  Ln(s)

are in the range of –2.2 to –2.4 V except for Eu for which the value is – 2.0 V.

The carbides, Ln3C, Ln2C3 and LnC2 are formed when the metals are heated with carbon.

ACTINODES

GENERAL ELECTRONIC CONFIGURATION

5 f1 – 14 6 d0 – 1 7s2

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How to Learn the Elements

Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

Atomic Number Elements Symbol 5f 6d 7s

89 Actinium Ac 0 1 2
90 Thorium Th 0 2 2
91 Protactinium Pa 2 1 2
92 Uranium U 3 1 2
93 Neptunium Np 4 1 2
94 Plutonium Pu 6 0 2
95 Americium Am 7 0 2
96 Curium Cm 7 1 2
97 Berkelium Bk 9 0 2
98 Californium Cf 10 0 2
99 Einstenium Es 11 0 2
100 Fermium Fm 12 0 2
101 Mendelevium Md 13 0 2
102 Nobelium No 14 0 2
103 Lawrencium Lr 14 1 2

OXIDATION STATES
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
3 3 3 3 3 3 3 3 3 3 3 3 3 3
4 4 4 4 4 4 4 4
5 5 5 5 5
6 6 6 6
7 7

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GENERAL CHARACTERISTICS
1. All are paramagnetic

2. All are silvery white metal

3. They get tarnished on exposure to alkali

4. All are radioactive (Atomic no 92 onwards are elements are called transuranic elements)

5. They react with boiling water to form mixture of oxides & hydrides

6. All react with non metals at moderate temp.

7. All react with HCl but effect with HNO3 is small due to formation of oxide layers.

ATOMIC AND IONIC SIZE

1. L to R size decrease due to increase in ENC due to Actinide contraction (poor screening of
5f electrons)
2. Contraction is greater than 4f series.

APPLICATION OF D & F BLOCK ELEMENTS

1. Iron and steels production is based on the reduction of iron oxides, the removal of
impurities and the addition of carbon and alloying metals such as Cr, Mn and Ni.

2. TiO for the pigment industry and MnO2 for use in dry battery cells.

3. The battery industry also requires Zn and Ni/Cd.

4. V2O5 catalyses the oxidation of SO2 in the manufacture of sulphuric acid.

5. TiCl4 with A1(CH3)3 for Ziegler catalysts used to manufacture polyethylene (polythene).

6. Iron catalysts are used in the Haber process for the production of ammonia from N2/H2
mixtures

7. Nickel catalysts enable the hydrogenation of fats to proceed

8. Wacker process for the oxidation of ethyne to ethanal is catalysed by PdCl2.

9. The photography - light-sensitive properties of AgBr.

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