The d-Block Elements

1
 Introduction
• d-block elements
🡺 locate between the s-block and
p-block
🡺 known as transition elements
🡺 occur in the fourth and subsequent
periods of the Periodic Table

2
 d-block elements
period 4

period 5

period 6

period 7

3
 Introduction
Transition elements are elements that
contain an incomplete d sub-shell (i.e. d1
to d9) in at least one of their oxidation
states in compounds.

3d0

3d10
4
 Introduction
Cd and Zn are not transition elements
because
They form compounds with only one
oxidation state in which the d sub-shell
are NOT incomplete.
Cd → Cd2+ 4d10 Zn → Zn2+ 3d10

5
 The first transition series
the first horizontal row of the d-block elements
6
 Characteristics of transition elements
(d-block vs s-block)

1. Physical properties vary slightly with atomic

number across the series (cf. s-block and
p-block elements)
2. Higher m.p./b.p./density/hardness than
s-block elements of the same periods.
3. Variable oxidation states
(cf. fixed oxidation states of s-block
elements)
7
 Characteristics of transition elements

4. Formation of coloured compounds/ions

(cf. colourless ions of s-block elements)
5. Formation of complexes
6. Catalytic properties

8
 Electronic Configurations

The building up of electronic configurations

of elements:
🡺 Aufbau principle
🡺 Pauli exclusion principle
🡺 Hund’s rule

9
 Electronic Configurations
• 3d and 4s sub-shells are very close to
each other in energy.
• Relative energy of electrons in
sub-shells depends on the effective
nuclear charge they experience.
• Electrons enter 4s sub-shell first
• Electrons leave 4s sub-shell first

10
 Cu Cu2+

After
‘electrons’ left
the atom
Relative energy levels of orbitals
in atom and in ion
11
 Electronic Configurations
• Valence electrons in the inner 3d orbitals

• Examples:
🡺🡺 The electronic configuration of
scandium: 1s22s22p63s23p63d14s2
🡺 The electronic configuration of zinc:
1s22s22p63s23p63d104s2

12
 Electronic configurations of the first series of the
d-block elements
Element Atomic number Electronic configuration
Scandium 21 [Ar] 3d 14s2
Titanium 22 [Ar] 3d 24s2
Vanadium 23 [Ar] 3d 34s2
Chromium 24 [Ar] 3d 54s1
Manganese 25 [Ar] 3d 54s2
Iron 26 [Ar] 3d 64s2
Cobalt 27 [Ar] 3d 74s2
Nickel 28 [Ar] 3d 84s2
Copper 29 [Ar] 3d 104s1

13
Zinc 30 [Ar] 3d 104s2
 • A half-filled or fully-filled d sub-shell
has extra stability

14
 d -Block Elements as Metals

• d-Block elements are typical metals

Physical properties of d-Block elements :

🡺 good conductors of heat and electricity
🡺 hard
🡺 strong
🡺 malleable and ductile

15
 d -Block Elements as Metals
• Physical properties of d-Block elements:
🡺 lustrous
🡺 high melting points and boiling points

• Exceptions : Mercury
🡺 low melting point
🡺 liquid at room temperature and
pressure
16
 d -Block Elements as Metals
• d-block elements
🡺 extremely useful as construction
materials
🡺 strong and unreactive

17
 d -Block Elements as Metals
• Iron

🡺 used for construction and making

machinery nowadays
🡺 abundant
🡺 easy to extract

18
 d -Block Elements as Metals
• Iron

🡺 corrodes easily
🡺 often combined with other
elements to form steel
∴ harder and higher resistance to
corrosion

19
 d -Block Elements as Metals
• Titanium
Corrosion resistant, light, strong and
withstand large temperature changes

🡺 used to make aircraft and space

shuttles
🡺 expensive

20
 d -Block Elements as Metals
• The similar atomic radii of the
transition metals facilitate
🡺 formation of substitutional alloys
🡺 the atoms of one element to
replace those of another element
🡺 modify their solid structures and
physical properties

21
 d -Block Elements as Metals
• Chromium
🡺 confers inertness to stainless steel

• Manganese
confers hardness & wearing resistance to
its alloys
e.g. duralumin : alloy of Al with
Mn/Mg/Cu

22
 Atomic Radii and Ionic Radii
• Two features can be observed:
1. The d-block elements have smaller
atomic radii than the s-block elements

2. The atomic radii of the d-block

elements do not show much variation
across the series

23
 Atomic Radii and Ionic Radii

Variation in atomic radius

of the first 36 elements

24
25
26
 (i) ↑ in nuclear charge
(ii) ↑ in shielding effect (repulsion between
e -)

(i) ≈ (ii)

(i) > (ii) (ii) > (i)

27
 Atomic Radii and Ionic Radii
• At the beginning of the series
🡺 atomic number ↑
🡺 effective nuclear charge ↑
🡺 the electron clouds are pulled
closer to the nucleus
🡺 atomic size ↓

28
 • In the middle of the series
🡺 more electrons enter the inner
3d sub-shell
🡺 The inner 3d electrons shield the
outer 4s electrons effectively

🡺 the effective nuclear charge

experienced by 4s electrons increases
very slowly
🡺 only a slow decrease in atomic radius
in this region
29
 Atomic Radii and Ionic Radii
• At the end of the series
🡺 the screening and repulsive effects
of the electrons in the 3d sub-
shell become even stronger
🡺 Atomic size ↑

30
 Comparison of Some Physical and
Chemical Properties between the
d-Block and s-Block Elements
• Many of the differences in physical and
chemical properties between the d-block
and s-block elements
🡺 explained in terms of their differences
in electronic configurations and
atomic radii

31
 1. Density

Densities (in g cm–3) of the s-block elements and

the first series of the d-block elements at 20°C
32
 1. Density
• d-block > s-block
🡺 1. the atoms of the d-block elements
are generally smaller in size
2. more closely packed
(fcc/hcp vs bcc in group 1)
3. higher atomic mass

33
 1. Density

• The densities
🡺 generally increase across the first
series of the d-block elements
🡺 1. general decrease in atomic
radius across the series
2. general increase in atomic mass
across the series

34
 2. Ionization Enthalpy

K → Ca (sharp ↑) ; Ca → Sc (slight ↑)

Ionization enthalpy (kJ mol–1)

Element
1st 2nd 3rd 4th
K 418 3 070 4 600 5 860
Ca 590 1 150 4 940 6 480
Sc 632 1 240 2 390 7 110
Ti 661 1 310 2 720 4 170
V 648 1 370 2 870 4 600
Cr 653 1 590 2 990 4 770
35
 2. Ionization Enthalpy
Sc → Cu (slight ↑) ; Cu → Zn (sharp ↑)
Ionization enthalpy (kJ mol–1)
Element
1st 2nd 3rd 4th
Cr 653 1 590 2 990 4 770
Mn 716 1 510 3 250 5 190
Fe 762 1 560 2 960 5 400
Co 757 1 640 3 230 5 100
Ni 736 1 750 3 390 5 400
Cu 745 1 960 3 550 5 690
Zn 908 1 730 3 828 5 980
36
 2. Ionization Enthalpy

• The first ionization enthalpies of the

d-block elements
🡺 greater than those of the s-block
elements in the same period of the
Periodic Table
🡺 1. The atoms of the d-block
elements are smaller in size
2. greater effective nuclear charges
37
 Sharp ↑ across periods 1, 2 and 3
Slight ↑ across the transition series

38
 2. Ionization Enthalpy

• Going across the first transition series

🡺 the nuclear charge of the elements
increases
🡺 additional electrons are added to
the ‘inner’ 3d sub-shell

39
 2. Ionization Enthalpy

• The screening effect of the additional

3d electrons is significant

• The effective nuclear charge experienced

by the 4s electrons increases very slightly
across the series
• For 2nd, 3rd, 4th… ionization enthalpies,
similar gradual ↑ across the series are
observed.
40
 Electron has to be removed from
completely filled 3p subshell

3d5

3d5
3d10
3d5 d10/s2

41
 2. Ionization Enthalpy

• The first few successive ionization

enthalpies for the d-block elements
🡺 do not show dramatic changes
🡺 4s and 3d energy levels are close to
each other

42
 Difficult to remove e- from fully- or half-filled sub-shells

d 5 Fe3+

Mn2+

Cr+

43
 3. Melting Points and Hardness
d-block >> s-block
🡺 1. both 4s and 3d e- are involved in the
formation of metal bonds
2. d-block atoms are smaller

1541 1668 1910 1907 1246 1538 1495 1455 1084 419

44
 3. Melting Points and Hardness
K has an exceptionally small m.p. because it has an
more open b.c.c. structure.

1541 1668 1910 1907 1246 1538 1495 1455 1084 419

45
Sc Ti V Cr Mn Fe Co Ni Cu Zn
1541 1668 1910 1907 1246 1538 1495 1455 1084 419

🡺 Unpaired electrons are relatively

more involved in the sea of electrons

46
Sc Ti V Cr Mn Fe Co Ni Cu Zn
1541 1668 1910 1907 1246 1538 1495 1455 1084 419
3d 4s
Sc ↑ ↑↓

Ti ↑ ↑ ↑↓

V ↑ ↑ ↑ ↑↓

1. m.p. ↑ from Sc to V due to the ↑ of

1 3
unpaired d-electrons (from d to d )
47
Sc Ti V Cr Mn Fe Co Ni Cu Zn
1541 1668 1910 1907 1246 1538 1495 1455 1084 419
3d 4s
Fe ↑↓ ↑ ↑ ↑ ↑ ↑↓

Co ↑↓ ↑↓ ↑ ↑ ↑ ↑↓

Ni ↑↓ ↑↓ ↑↓ ↑ ↑ ↑↓

2. m.p. ↓ from Fe to Zn due to the ↓ of

unpaired d-electrons (from 4 to 0)
48
Sc Ti V Cr Mn Fe Co Ni Cu Zn
1541 1668 1910 1907 1246 1538 1495 1455 1084 419

3. Cr has the highest no. of unpaired

electrons but its m.p. is lower than V.
3d 4s
Cr ↑ ↑ ↑ ↑ ↑ ↑

It is because the electrons in the

half-filled d-subshell are relatively
less involved in the sea of electrons.
49
Sc Ti V Cr Mn Fe Co Ni Cu Zn
1541 1668 1910 1907 1246 1538 1495 1455 1084 419

4. Mn has an exceptionally low m.p.

because it has the very open cubic
structure.
Why is Hg a liquid at room conditions ?
All 5d and 6s electrons are paired up
and the size of the atoms is much
larger than that of Zn.
50
 3. Melting Points and Hardness

• The hardness of a metal dependent on

🡺 the strength of the metallic bonds

• The metallic bonds of the d-block

elements are stronger than those of the
s-block elements
∴ much harder than the s-block
elements
51
 Mohs scale : - A measure of hardness

Talc Diamond
0 10
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn
0.5 1.5 3.0 4.5 6.1 9.0 5.0 4.5 -- -- 2.8 2.5

52
 4. Reaction with Water

• In general, the s-block elements

🡺 react vigorously with water to form
metal hydroxides and hydrogen
• The d-block elements
🡺 react very slowly with cold water
🡺 react with steam to give metal oxides
and hydrogen
53
d-block compounds vs s-block compounds
A Summary : -
Ions of d-block metals have higher charge density
⇒ more polarizing
⇒ 1. more covalent in nature
2. less soluble in water
3. less basic (more acidic)
e.g. Fe(OH)3 < Fe(OH)2 << NaOH

54
 Variable Oxidation States
• One of the most striking properties
🡺 variable oxidation states

• The 3d and 4s electrons are

🡺 in similar energy levels
🡺 available for bonding

55
 Variable Oxidation States
• Elements of the first transition series
🡺 react with other elements to form
compounds
🡺 form ions of roughly the same
stability by losing different
numbers of the 3d and 4s electrons

56
 Oxidation states of the elements of the first transition
series in their oxides and chlorides
Oxidation
Oxides / Chloride
states
Cu2O
+1
Cu2Cl2
TiO VO CrO MnOFeO CoO NiO CuO ZnO
+2 TiCl2 VCl2 CrCl2 MnCl2 FeCl2 CoCl2 NiCl2 CuCl2
ZnCl2
Sc2O3 Ti2O3 V2O3 Cr2O3 Mn2O3 Fe2O3 Ni2O3 • xH2O
+3
ScCl3 TiCl3 VCl3 CrCl3 MnCl3 FeCl3
TiO2 VO2 MnO2
+4
TiCl4 VCl4 CrCl4

+5 V 2O 5

+6 CrO3
57
+7 Mn2O7
 Oxidation states of the elements of the first transition
series in their compounds
Element Possible oxidation state
Sc +3
Ti +1 +2 +3 +4
V +1 +2 +3 +4 +5
Cr +1 +2 +3 +4 +5 +6
Mn +1 +2 +3 +4 +5 +6 +7
Fe +1 +2 +3 +4 +5 +6
Co +1 +2 +3 +4 +5
Ni +1 +2 +3 +4 +5
Cu +1 +2 +3
58 Zn +2
 1. Scandium and zinc do not exhibit variable
oxidation states

• Scandium of the oxidation state +3

🡺 the stable electronic configuration
of argon (i.e. 1s22s22p63s23p6)

• Zinc of the oxidation state +2

🡺 the stable electronic configuration
of [Ar] 3d10
59
 2. (a) All elements of the first transition
series (except Sc) can show an
oxidation state of +2

(b) All elements of the first transition

series (except Zn) can show an
oxidation state of +3

60
 3. Manganese has the highest oxidation
state +7

E.g. MnO4-, Mn2O7

Mn7+ ions do not exist.

61
 The +7 state of Mn does not mean that
all 3d and 4s electrons are removed
from Mn to give Mn7+.
Instead, Mn forms covalent bonds with
oxygen atoms by making use of its half
filled orbitals

62
 Draw the structure of Mn2O7

63
 3. Manganese has the highest oxidation
state +7

• The highest oxidation state

🡺 not be greater than the total
number of the 3d and 4s electrons
🡺 inner electrons (3s, 3p…) are not
involved in covalent bond
formation
64
 4. For elements after manganese, there is a
reduction in the number of possible
oxidation states

• The 3d electrons are held more firmly

🡺 the decrease in the number of
unpaired electrons
🡺 the increase in nuclear charge

65
 5. The relative stability of various oxidation
states is correlated with the stability of
electronic configurations
• Electronic configurations with half-filled
or fully-filled sub-shell has extra stability
Stability : - : Ti4+ > Ti3+
Ti4+(aq) > Ti3+(aq)
Ar [Ar] 3d1

Ti4+(g) < Ti3+(g)

66
 5. The relative stability of various oxidation
states is correlated with the stability of
electronic configurations

Stability : - Mn2+(aq) > Mn3+(aq)

[Ar] 3d5 [Ar] 3d4
Fe3+(aq) > Fe2+(aq)
[Ar] 3d5 [Ar] 3d6

67
 5. The relative stability of various oxidation
states is correlated with the stability of
electronic configurations

Stability : -

Zn2+(aq) > Zn+(aq)

[Ar] 3d10 [Ar] 3d104s1

68
 Colours of aqueous ions of vanadium of
different oxidation states
Oxidation state of Colour in
Ion
vanadium in the ion aqueous solution
V2+(aq) +2 Violet
V3+(aq) +3 Green
VO2+(aq) +4 Blue
VO2+(aq) +5 Yellow

69
 Colours of compounds or ions of manganese in
different oxidation states
Oxidation state of
Ion Colour
manganese in the ion
Mn2+ +2 Very pale pink
Mn(OH)3 +3 Dark brown
Mn3+ +3 Red
MnO2 +4 Black
MnO42– +6 Green
MnO4– +7 Purple

70
 (a) (b) (c)

Mn2+(aq) Mn(OH)3(aq) MnO2(s)

Colours of compounds or ions of manganese in
differernt oxidation states: (a) +2; (b) +3; (c) +4
71
 (d) (e)

MnO42–(aq) MnO4–(aq)
Colours of compounds or ions of manganese in
differernt oxidation states: (d) +6; (e) +7
72
 Oxidizing power of Mn(VII) depends on
pH of the solution
In an acidic medium (pH 0)

MnO4–(aq) + 8H+(aq) + 5e– Mn2+(aq) + 4H2O(l)

= +1.51 V

In an alkaline medium (pH 14)

MnO4–(aq) + 2H2O(l) + 3e– MnO2(s) + 4OH−

(aq) = +0.59 V
73
Why is the Eo of MnO4− MnO42− Eo = +0.56V
not affected by pH ?

MnO4−(aq) + e− MnO42− Eo = +0.56V

The reaction does not involve H+(aq) nor OH−(aq)

74
MnO2 is oxidized to MnO42− in alkaline medium
2MnO2 + 4OH− + O2 → 2MnO42− + 2H2O
Preparing MnO4− from MnO2

1. 2MnO2 + 4OH− + O2 → 2MnO42− + 2H2O

2. 3MnO42− + 4H+ → 2MnO4− + MnO2 + 2H2O
3. Filter the resulting mixture to remove MnO2

75
 Formation of Complexes
• Another striking feature of the
d-block elements is the formation of
complexes

76
 Coloured Ions
• Most of the d-block metals
🡺 form coloured compounds

🡺 due to the presence of the

incompletely filled d orbitals in the
d-block metal ions
Which aqueous transition metal ion(s) is/are
not coloured ? 2+ + 10 3+ 4+ 0
Zn , Cu (3d ), Sc , Ti (3d )
77
 Colours of some d-block metal ions in aqueous solutions
Number of unpaired
d-Block metal Colour in
electrons in 3d
ion aqueous solution
orbitals
Sc3+ Colourless
Ti4+ Colourless
0
Zn2+ Colourless
Cu+ Colourless
Ti3+ Purple
1 V4+ Blue
78 Cu2+ Blue
 Colours of some d-block metal ions in aqueous solutions
Number of unpaired
d-Block metal Colour in
electrons in 3d
ion aqueous solution
orbitals
V3+ Green
2
Ni2+ Green
V2+ Violet
3 Cr3+ Green
Co2+ Pink

79
 Colours of some d-block metal ions in aqueous solutions
Number of unpaired
d-Block metal Colour in
electrons in 3d
ion aqueous solution
orbitals
Cr2+ Blue
4 Mn3+ Violet
Fe2+ Green
Mn2+ Very pale pink
5
Fe3+ Yellow

80
 Co2+(aq) Zn2+(aq) Fe3+(aq)

Colours of some d-block metal ions in aqueous solutions

81
 In gaseous state,
the five 3d orbitals are degenerate
i.e. they are of the same energy level

In the presence of ligands,

The five 3d orbitals interact with the
orbitals of ligands and split into two groups
of orbitals with slightly different energy
levels
82
 distributes along x and y axes
distributes along z axis
Interact more strongly with
the orbitals of ligands

The splitting of the degenerate 3d orbitals of

a d-block metal ion in an octahedral complex

83
 • Criterion for d-d transition : -
presence of unpaired d electrons in
the d-block metal atoms or ions
d-d transition is possible for
3d1 to 3d9 arrangements
d-d transition is NOT possible for
3d0 and 3d10 arrangements

84
 ↑↓↑

Cu2+

↑↓↑↓↑↓

3d9 : d-d transition is possible

85
 Sc3+

3d0 : d-d transition NOT possible

86
 Potassium dichromate
It is prepared in two steps :

(i) First the chromite ore ( FeCr2O4) is fused with

Na2CO3 or K2CO3 in free access of air

4 FeCr2O4 + 8 Na2CO3 + 7O2 8 Na2CrO4

+ 2 Fe 2O3

87 + 8 CO2
 STEP : 02
(ii) The yellow soln of sodium
chromate is filtered and acidified
with H2SO4 to give a soln. from
which orange sodium dichromate
can be crystallized.

+
2 Na2CrO4 + 2H Na2Cr2O7
+
+2Na + H2O

88
 Potassium dichromate to Sodium
dichromate
Sodium dichromate is more soluble
than Potassium dichromate
therefore K2Cr2O7 is prepared by treating
Na2Cr2O7 with KCl.

Na2Cr2O7 + KCl K2Cr2O7 + 2NaCl

89
 Chromate and Dichromate ions
CrO42- 2-
O

Cr
O
O
O

90 Chromate ion
 Dichromate ion
2-
Cr2O7
2-
pm
O 17
9 O
O
1260
Cr Cr O
O

16
3
pm
O O
91
 Chemical properties
K2Cr2O7 and Na2Cr2O7 are strong
oxidising agents :
In acidic solution its oxidising action
can be represented as :

Cr2O72- +14H+ +6e- 2Cr3+ + 7 H2O

(E =1.33V)
92