The d-Block Elements

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 Introduction

• d-block elements
• locate between the s-block and p-block
• contains the element group 3-12.
• These groups correspond to the filling of the
atomic  d-orbital subshell of the second outermost
shell (inside an outermost shell only containing 1 or
2 s-orbital electrons) with electron configurations
ranging from s2d1 (Group 3) to s2d10 (Group 12).

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 d-Block elements

3
 d-block elements
period 4

period 5

period 6

period 7

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

Co : [Ar] 4s2 3d 7
Co2+: [Ar] 3d 7
Co3+: [Ar] 3d 6

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 Sc and Zn are not transition elements
because
They form compounds with only one
oxidation state in which the d sub-shell are
NOT incomplete.
Sc  Sc3+ 3d0 Zn  Zn2+ 3d10

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 The first transition series
the first horizontal row of the d-block elements
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 Electronic Configurations

The building up of electronic configurations of

elements follow:
 Aufbau principle
 Pauli exclusion principle No two electrons in an atom
can have identical quantum
numbers
 Hund’s rule

Hund's Rule states that:

-Every orbital in a sublevel is singly occupied before any orbital is doubly
occupied.
-All of the electrons in singly occupied orbitals have the same spin (to
8 maximize total spin).
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 Aufbau principle

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 • 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

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 ELECTRON CONFIGURATION OF TRANSITION
METALS AND THEIR IONS

 Example: How you write electron configuration for 27Co?

1s 2s 2p 3s 3p 4s 3d

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Co: 1s2 2s2 2p6 3s2 3p6 4s2 3d7 OR [Ar] 4s2 3d7

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 ELECTRON CONFIGURATION OF TRANSITION
METALS AND THEIR IONS

 Example: How you write electron configuration for Co2+ ?

1s 2s 2p 3s 3p 4s 3d

Co2+: 1s2 2s2 2p6 3s2 3p6 4s0 3d7 OR [Ar] 3d7

NOT [Ar] 4s2 3d5

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  Exercise: Write the electron configuration of Fe2+ and
Fe3+.

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 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
Zinc 30 [Ar] 3d 104s2

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 • A half-filled or fully-filled d sub-shell
has extra stability

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 Characteristics of transition elements
(d-block metals vs s-block metals)

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 metals)

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 4. Formation of coloured compounds/ions
(cf. colourless ions of s-block elements)

5. Formation of complexes
6. Catalytic properties

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 1-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

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20
21
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 On moving across the Period,
(i) Nuclear charge 
(ii) Shielding effect (repulsion between e-) 

(i)  (ii)

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

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 • At the beginning of the series
 atomic number 
 effective nuclear charge 
 the electron clouds are pulled
closer to the nucleus
 atomic size 

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 • 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
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 • At the end of the series
 the screening and repulsive effects
of the electrons in the 3d sub-
shell become even stronger
 Atomic size 

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 2-Melting Points
Why d-block elements are higher than 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

MP is depend to the number of paired electrons

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 For example: why MP is increase from Sc to V?

3d 4s
Sc  

Ti   

V    

m.p.  from Sc to V due to the  of unpaired d-electrons

(from d1 to d3)

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 3-Hardness

• The hardness of a metal depends 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

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 3-Variable of oxidation states
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
Zn +2

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 Examples of variable oxidation states of
manganese

• Manganese
 show oxidation states of +2, +3,
+4, +5, +6 and +7 in its compounds
• The most common oxidation states
 +2, +4 and +7

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 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
MnO43 +5 Bright blue
MnO42– +6 Green
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MnO4– +7 Purple
 (a) (b) (c)

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

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

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 (d) (e)

MnO42–(aq) MnO4–(aq)
Colours of compounds or ions of manganese in
different oxidation states: (d) +6; (e) +7

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 Examples of variable oxidation states of
vanadium

Zn Zn
VO2 (aq) 
+
conc. HCl
VO (aq) 
2+
conc. HCl
yellow blue
Zn
V (aq) 
3+
conc. HCl
V 2+
(aq)
green violet

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(a) (b) (c) (d)

VO2+(aq) VO2+(aq) V3+(aq) V2+(aq)

Colours of aqueous solutions of compounds containing
vanadium in four different oxidation states:
(a) +5; (b) +4; (c) +3; (d) +2
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 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 V2O5

+6 CrO3

37 +7
Mn2O7
 d -Block Elements as Metals
• d-Block elements are typical metals

Physical properties of d-Block elements :

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

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 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
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 d -Block Elements as Metals
• d-block elements
 extremely useful as construction
materials
 strong and unreactive

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 d -Block Elements as Metals
• Iron

 used for construction and making

machinery nowadays
 abundant
cheap
 easy to extract

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 d -Block Elements as Metals
• Iron
 corrodes easily
 often combined with other
elements to form steel
 harder and more resistant to
corrosion

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

 used to make aircraft and space

shuttles
 expensive

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

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 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

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 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

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 2K(s) + 2H2O(l)  2KOH(aq) + H2(g)

2Na(s) + 2H2O(l)  2NaOH(aq) + H2(g)

Ca(s) + 2H2O(l)  Ca(OH)2(s) + H2(g)

Zn(s) + H2O(g)  ZnO(s) + H2(g)

3Fe(s) + 4H2O(g)  Fe3O4(s) + 4H2(g)

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