Unsur Blok-D

The d-Block Elements
1
Why we study the Transition
Metals
Transition metals are found in nature
Rocks and minerals contain transition
metals
The color of many gemstones is due to the
presence of transition metal ions
Rubies are red due to Cr
Sapphires are blue due to presence of Fe and Ti
Many biomolecules contain transition
metals that are involved in the functions of
these biomolecules
Vitamin B12 contains Co
Hemoglobin, myoglobin, and cytochrome C
2 contain Fe
Why we study the Transition
Metals
Transition metals and their
compounds have many useful
applications
Fe is used to make steel and
stainless steel
Ti is used to make lightweight alloys
Transition metal compounds are
used as pigments
TiO2 = white
PbCrO4 = yellow
3
Fe4[Fe(CN)6]3 (prussian blue)= blue
Introduction
d-block elements
The elements of periodic table
belonging to group 3 to 12 are known
as d-Block elements. because in these
elements last electron enters in d sub
shell or d orbital
locate between the s-block and p-block
occur in the fourth and subsequent
periods of the Periodic Table
4
d-block
elements
period
4
period
5
period
6
period
7
6
Introduction
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.
3d0
3d10
7
How are d - Block Elements
&
Transition elements
different?
Not all d block elements are
transition elements but all
transition elements are d-block
elements
Not all d block elements are
transition elements because d
block elements like Zinc have full
d10 configuration in their ground
state as well as in their common
8 oxidation state which is not
according to definition of transition
Introduction
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
9
Introduction
Cu 3d
+ 10
not transitional
Cu
Cu2+
3d 9
transitional
10
Group 7 Presentation
1. Which of the d-block elements may not be
regarded as the transition elements?
2. Why Zn, Cd and Hg are not considered as
transition elements.
3. Copper atom has completely filled d orbital
(3d10) in its ground state, yet it is transition
element. Why
4. Silver atom has completely filled d orbital
(4d10) in its ground state, yet it is transition
element. Why
5. Why the very name transition given to the
elements of d-block .
Answers
1. Zn, Cd and Hg
2. Because they do not have vacant d-orbitals neither

in the atomic state nor in any stable oxidation
state.
3. Copper (Z = 29) can exhibit +2 oxidation state

wherein it will have incompletely filled d-orbitals
(3d), hence a transition element.
4. Silver (Z = 47) can exhibit +2 oxidation state

wherein it will have incompletely filled d-orbitals
(4d), hence a transition element.
5. The very name transition given to the elements of

d-block is only because of their position between s
and p block elements.
The first transition series
the first horizontal row of the d-block elements
14
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)
15
Characteristics of transition elements
4. Formation of coloured compounds/ions

(cf. colourless ions of s-block elements)
5. Formation of complexes
6. Catalytic properties
16
Electronic Configurations
The building up of electronic configurations

of elements follow:
Aufbau principle
Hunds rule
Pauli exclusion principle
17
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
18
Cu Cu2+
Relative energy levels of orbitals

in atom and in ion
19
Valence electrons in the inner 3d orbitals
Examples:
The electronic configuration of
scandium: 1s22s22p63s23p63d14s2
The electronic configuration of zinc:
1s22s22p63s23p63d104s2
20
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
21
A half-filled or fully-filled d sub-shell
has extra stability
22
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
23
Physical properties of d-Block elements:
lustrous
high melting points and boiling points
Exceptions : Mercury
low melting point
liquid at room temperature and
pressure
24
d-block elements
extremely useful as construction
materials
strong and unreactive
25
Iron
used for construction and making

machinery nowadays
abundant
cheap
easy to extract
26
Iron
corrodes easily
often combined with other
elements to form steel
harder and more resistant to
corrosion
27
Titanium
Corrosion resistant, light, strong and
withstand large temperature changes
used to make aircraft and space

shuttles
expensive
28
Chromium
confers inertness to stainless steel
Manganese
confers hardness & wearing resistance to
its alloys
e.g. duralumin : alloy of Al with
Mn/Mg/Cu
29
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
30
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
31
Variation in atomic radius

of the first 36 elements
32
33
34
On moving across the Period,
(i) Nuclear charge
(ii) Shielding effect (repulsion between e-)
(i) (ii)
(i) > (ii) (ii) > (i)
35
At the beginning of the series
atomic number
effective nuclear charge
the electron clouds are pulled
closer to the nucleus
atomic size
36
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
37
At the end of the series
the screening and repulsive effects
of the electrons in the 3d sub-
shell become even stronger
Atomic size
38
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
39
1. Density
Densities (in g cm3) of the s-block elements and

the first series of the d-block elements at 20C
40
1. Density
d-block > s-block
the atoms of the d-block elements
1. are generally smaller in size
2. are more closely packed
(fcc/hcp vs bcc in group 1)
3. have higher relative atomic masses
41
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
42
2. Ionization Enthalpy
K Ca (sharp ) ; Ca Sc (slight
)
Ionization enthalpy (kJ mol1)
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
43
Sc Cu (slight ) ; Cu Zn (sharp )
Ionization enthalpy (kJ mol1)
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
44
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
45
Sharp across periods 1, 2 and 3
Slight across the transition series
46
Going across the first transition series

the nuclear charge of the elements
increases
additional electrons are added to
the inner 3d sub-shell
47
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,
slight and gradual across the series
are observed.
48
Electron has to be removed from
completely filled 3p subshell
3d5 Fe3+
3d5 Mn2+
3d10
3d5 Cr+
d10/s2
49
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
50
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
51
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
52
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
53
1541 1668 1910 1907 1246 1538 1495 1455 1084 419
3d 4s
Sc
Ti
1. m.p. from Sc to V due to the of

unpaired d-electrons (from d1 to d3)
54
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)
55
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.
56
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.
57
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
58
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
59
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
60
4. Reaction with Water
2K(s) + 2H2O(l) 2KOH(aq) + H2(g)
2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g)
Ca(s) + 2H2O(l) Ca(OH)2(aq) + H2(g)
Zn(s) + H2O(g) ZnO(s) + H2(g)
3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g)
61
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)
Basicity : Fe(OH)3 < Fe(OH)2 << NaOH
Charge density : Fe3+ > Fe2+ > Na+

62
d-block compounds vs s-block compounds
A Summary : -
4. less thermally stable e.g. CuCO3 <<

Na2CO3
5. tend to exist as hydrated salts
e.g. CuSO4.5H2O, CoCl2.2H2O
6. hydrated ions undergo hydrolysis more
easily
acidic
e.g. [Fe(H 2 O)6 ]3+
(aq) + H 2 O [Fe(OH)(H 2 O)5 ]2+
(aq)
+ H3O+
63
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
64
Variable Oxidation States
Elements of the first transition series
form ions of roughly the same
stability by losing different
numbers of the 3d and 4s electrons
65
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
+7 Mn2O7
66
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
Zn +2
67
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
68
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
69
3. Manganese has the highest oxidation
state +7
E.g. MnO4-, Mn2O7
Mn7+ ions do not exist.
70
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 O
Mn -
O
O
O
71
Draw the structure of Mn2O7
O O
Mn Mn
O
O O
O O
72
3. Manganese has the highest oxidation
state +7
The highest possible oxidation state
= the total no. of the 3d and 4s electrons
inner electrons (3s, 3p) are not
involved in covalent bond formation
73
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
74
5. The relative stability of various
oxidation states is correlated with the
stability of electronic configurations
Stability : - Mn2+(aq) > Mn3+(aq)
Major factor [Ar] 3d5 [Ar] 3d4
Fe3+(aq) > Fe2+(aq)

[Ar] 3d5 [Ar] 3d6
Major factor H ohydration: Fe3+ > Fe2+
75
5. The relative stability of various
oxidation states is correlated with the
stability of electronic configurations
Stability :
- 2+
Zn (aq) > Zn+(aq)
[Ar] 3d10 [Ar] 3d104s1
Major factor H ohydration: Zn2+ > Zn+
76
1. Variable Oxidation States of Vanadium and
their Interconversions
The compounds of vanadium, vanadium
oxidation states of +2, +3, +4 and +5
forms ions of different oxidation
states
show distinctive colours in aqueous
solutions
77
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
78
In an acidic medium
the vanadium(V) state usually
occurs in the form of VO2+(aq)
dioxovanadium(V) ion
the vanadium(IV) state occurs in
the form of VO2+(aq)
oxovanadium(IV) ion
79
In an alkaline medium
the stable form of the vanadium(V)
state is
VO3(aq), metavanadate(V) or
VO43(aq), orthovanadate(V), in
strongly alkaline medium
80
Compounds with vanadium in its highest
oxidation state (i.e. +5)
strong oxidizing agents
81
Vanadium of its lowest oxidation state
(i.e. +2)
in the form of V2+(aq)
strong reducing agent
easily oxidized when exposed to air
82
Interconversions of the common
oxidation states of vanadium can be
carried out readily in the laboratory
The most convenient starting material
ammonium metavanadate(V) (NH4VO3)
a white solid
the oxidation state of vanadium is +5
83
1. Interconversions of Vanadium(V) species
OH OH OH
VO2+(aq) V2O5(s) VO3(aq) VO43(aq)
H+ H+ H+
Yellow orange yellow colourless
Vanadium(V) can exist as cation as well as anion
84
OH OH OH
H+ H+ H+
In acidic medium In alkaline medium

Amphoteric
85
OH OH OH
H+ H+ H+

Amphoteric
Give the equation for the conversion : V2O5 VO2+
V2O5(s) + 2H+(aq) 2VO2+(aq) + H2O(l)
86
OH OH OH
H+ H+ H+

Amphoteric
Give the equation for the conversion : V2O5 VO3
V2O5(s) + 2OH(aq) 2VO3(aq) + H2O(l)
87
OH OH OH
H+ H+ H+

Amphoteric
Give the equation for the conversion : VO3 VO2+
VO3(aq) + 2H+(aq) VO2+(aq) + H2O(l)
88
H H H
O
H H O
O V5+ O H
H H
O
H H
8H2O
orthovanadate(V) ion VO43(aq) + 8H3O+

V5+ ions does not exist in water since it undergoes
vigorous hydrolysis to give VO43
The reaction is favoured in highly alkaline solution
89
V VO43(aq) orthovanadate(V) ion
Cr CrO42(aq) chromate(VI) ion
Mn MnO4(aq) manganate(VII) ion
Draw the structures of VO43, CrO42 and MnO4
O O
Cr Mn
O-
O-
O O
O- O
90
H H H
O
H H O
O V5+ O H
H H
O
H H
6H2O
Metavanadate(V) ion VO3(aq) + 6H3O+
The reaction is favoured in alkaline solution

VO3 is a polymeric anion like SiO32
91
Metavanadate(V) ion, (VO3)nn
92
H H H
O
H H O
O V5+ O H
H H
O
H H
4H2O
VO2+(aq) + 4H3O+
The reaction is favoured in acidic solution
93
2. The action of zinc powder and

concentrated hydrochloric acid
vanadium(V) ions can be reduced
sequentially to vanadium(II) ions
94
Zn Zn
VO2 (aq)
+
conc. HCl
VO (aq)
2+
conc. HCl
yellow blue
Zn
V (aq)
3+
conc. HCl
V2+(aq)
green violet
95
(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
96
The feasibility of the changes in oxidation
state of vanadium
can be predicted using standard
electrode potentials
Half reaction (V)

Zn2+(aq) + 2e Zn(s) 0.76
VO2+(aq) + 2H+(aq) + e VO2+(aq) + H2O(l) +1.00
VO2+(aq) + 2H+(aq) + e V3+(aq) + H2O(l) +0.34
V3+(aq) + e V2+(aq) 0.26
97
Under standard conditions
zinc can reduce
1. VO2+(aq) to VO2+(aq) >0
2. VO2+(aq) to V3+(aq) >0
3. V3+(aq) to V2+(aq) >0
98
2 (VO2+(aq) + 2H+(aq) + e
VO2+(aq) + H2O(l)) = +1.00 V
) Zn2+(aq) + 2e Zn(s) = 0.76 V
2VO2+(aq) + Zn(s) + 4H+(aq)

2VO2+(aq) + Zn2+(aq) + 2H2O(l)
= +1.76 V
99
2 (VO2+(aq) + 2H+(aq) + e
V3+(aq) + H2O(l)) = +0.34 V
) Zn2+(aq) + 2e Zn(s) = 0.76 V
2VO2+(aq) + Zn(s) + 4H+(aq)

2V3+(aq) + Zn2+(aq) + 2H2O(l)
= +1.10 V
100
2 (V3+(aq) + e V2+(aq))
= 0.26 V
) Zn2+(aq) + 2e Zn(s) = 0.76 V
2V3+(aq) + Zn(s) 2V2+(aq) + Zn2+(aq)

= +0.50 V
101
2. Variable Oxidation States of Manganese and
Manganese
show oxidation states of +2, +3,
+4, +5, +6 and +7 in its compounds
The most common oxidation states
+2, +4 and +7
102
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
103
MnO4 +7 Purple
(a) (b) (c)
Mn2+(aq) Mn(OH)3(aq) MnO2(s)

differernt oxidation states: (a) +2; (b) +3; (c) +4
104
(d) (e)
MnO42(aq) MnO4(aq)
differernt oxidation states: (d) +6; (e) +7
105
2. Variable Oxidation States of Manganese and
Manganese of the oxidation state +2
the most stable at pH 0
+1.50V 1.18V
Mn3+ Mn2+ Mn
+1.51V +1.23V
MnO4 MnO2
106
Mn(VII)
Explosive on heating and extremely oxidizing
+7 2 +6 +4 0
heat
2KMnO4 K2MnO4 + MnO2 + O2
in ON = 2(+2) = +4
in ON = (1) + (3) = 4
107
Mn(VII)
+7 2 light +4 0
4MnO4 + 4H+ 4MnO2 + 2H2O + 3O2
in ON = 6(+2) = +12
in ON = 4(3) = 12
The reaction is catalyzed by light

Acidified KMnO4(aq) is stored in amber bottle
108
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 a neutral or alkaline medium (up to pH 14)
MnO4(aq) + 2H2O(l) + 3e MnO2(s) + 4OH

(aq) = +0.59 V
109
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)
110
In an acidic medium (pH 0)
MnO4(aq) + 8H+(aq) + 5e Mn2+(aq) + 4H2O(l)
= +1.51 V
In a neutral or alkaline medium (up to pH 14)

MnO4(aq) + 2H2O(l) + 3e MnO2(s) + 4OH
(aq) = +0.59 V
Under what conditions is the following

conversion favoured?
MnO4(aq) + e MnO42 Eo = +0.56V
When [OH(aq)] > 1M
111
Predict if Mn(VI) Mn(VII) + Mn(IV) is feasible at
(i) pH 0 and (ii) pH 14
(1) MnO42(aq) + 4H+(aq) + 2e MnO2(s) + 2H2O(l) Eo = +2.26V
(2) MnO42(aq) + 2H2O(l) + 2e MnO2(s) + 4OH(aq) Eo = +0.60V
(3) MnO4 + e MnO42 Eo = +0.56V
At pH 0 (1) 2(3)
3MnO42(aq) + 4H+(aq) 2MnO4(aq) + MnO2(s) + 2H2O(l)
Eocell = +1.70V (feasible)
Mn(VI) is unstable in acidic medium
At pH 14 (2) 2(3)
3MnO42(aq) + 2H2O(l) 2MnO4(aq) + MnO2(s) + 4OH(aq)
Eocell = +0.04V (much less feasible)
112
Mn(IV) Oxidizing in acidic medium
MnO2(s) + 4H+(aq) + 2e Mn2+(aq) + 2H2O(l)

= 1.23 V
Used in the laboratory production of chlorine
MnO2(s) + 4HCl(aq) MnCl2(aq) + 2H2O(l) + Cl2(g)
113
Mn(IV) Reducing in alkaline medium
Oxidized to Mn(VI) in alkaline medium

2MnO2 + 4OH + O2 2MnO42 + 2H2O
114
MnO2 is oxidized to MnO42 in alkaline medium
2MnO2 + 4OH + O2 2MnO42 + 2H2O
Suggest a scheme to prepare MnO4 from MnO2
1. 2MnO2 + 4OH + O2 2MnO42 + 2H2O

2. 3MnO42 + 4H+ 2MnO4 + MnO2 + 2H2O
3. Filter the resulting mixture to remove MnO2
7B
115
Cu+(aq) + e Cu(s) Eo = +0.52V
Cu2+(aq) + 2e Cu(s) Eo = +0.34V
Cu2+(aq) is more stable than Cu+(aq)

The only copper(I) compounds which can be stable
in water are those which are
(i) insoluble (e.g. Cu2O, CuI, CuCl)
(ii) complexed with ligands other than water
e.g. [Cu(NH3)4]+ Cu+(aq) + e Cu(s)
Under these conditions, [Cu+(aq)]
116
Equil. Position shifts to left
Estimation of Cu2+ ions
2Cu2+(aq) + 4I(aq) 2CuI(s) + I2(aq)
unknown excess white fixed
I2(aq) + 2S2O32(aq) 2I(aq) + S4O62(aq)

standard solution
117
Formation of Complexes
Another striking feature of the
d-block elements is the
formation of complexes
118
A complex is formed when a central
metal atom or ion is surrounded by
other molecules or ions which form
dative covalent bonds with the central
metal atom or ion.
The molecules or ions that donate lone

pairs of electrons to form the dative
covalent bonds are called ligands.
119
A ligand
can be an ion or a molecule having
at least one lone pair of
electrons that can be donated to
the central metal atom or ion to
form a dative covalent bond
120
Complexes can be
electrically neutral Ni(CO)4
positively charged [Co(H2O)6]3+
negatively charged [Fe(CN)6]3
121
A co-ordination compound is either
a neutral complex e.g. Ni(CO)4
or made of
a complex ion and another ion
e.g. [Co(H2O)6]Cl3 [Co(H2O)6]3+ + 3Cl
K3[Fe(CN)6] 3K+ + [Fe(CN)6]3
122
Criteria for complex formation
1. Presence of vacant and low-energy 3d,
4s, 4p and 4d orbitals in the metal
atoms or ions to accept lone pairs from
ligands.
2. High charge density of the central
metal ions.
123
Diagrammatic representation of the formation of a complex
124
[Co(H2O)6]2+
Co : 3d 4s 4p 4d

Co2+ : 3d 4s 4p 4d

The six sp3d2 orbitals accept sp3d2 hybridisation

six lone pairs from six H2O.
Arranged octahedrally to
minimize repulsion between
dative
125 bonds.
1. Complexes with Monodentate Ligands
A ligand that forms one dative covalent

bond only is called a monodentate ligand.
Examples:
neutral CO, H2O, NH3
anionic Cl, CN, OH
126
127
In the formation of complexes, classify the
transition metal ion and the ligand as a Lewis acid
or base. Explain your answer briefly.
The transition metal ion is the Lewis acid since it

accepts lone pairs of electrons from the ligands
in forming dative covalent bonds.
The ligand is the Lewis base since it donates a
lone pair of electrons to the transition metal ion
in forming dative covalent bonds.
128
What is the oxidation state of the central metal ?
Cr3+ Zn2+
129
Co3+
130
Fe3+ Co2+
131
2. Complexes with Bidentate Ligands
A ligand that can form two dative covalent

bonds with a metal atom or ion is called a
bidentate ligand.
A ligand that can form more than one

dative covalent bond with a central metal
atom or ion is called a chelating ligand.
132
Ethylenediamine
(H2NCH2CH2NH2) Oxalate (C2O42)
Ethylenediamine oxalate ion (oxo)
(en)
The term chelate is derived from Greek, meaning claw.
The ligand binds with the metal like the great claw of
the lobster.
133
ethylenediamine
oxalate ion
134
3. Complexes formed by Multidentate Ligands
Ligands that can form more than two

dative covalent bonds to a metal atom
or ion are called multidentate ligands.
Some ligands can form as many as six
bonds to a metal atom or ion.
Example:
ethylenediaminetetraacetic acid
(abbreviated as EDTA)
135
EDTA forms six dative covalent bonds with
the metal ion through six atoms giving a
very stable complex.
hexadentate ligand
ethylenediaminetetraacetate ion
136
?
2
Fe2+
EDTA4
[FeEDTA]2
Structure of the complex ion formed by

iron(II) ions and EDTA
137
Uses of EDTA
1. Determining concentrations of metal ions
by complexometric titrations
e.g. determination of water hardness
2. In chelation therapy for mercury poisoning
and lead poisoning
Poisonous Hg2+ and Pb2+ ions are removed by
forming stable complexes with EDTA.
3. Preparing buffer solutions ( K a1 to K) a 4
4. As preservative to prevent catalytic

oxidation
138
of food by metal ions.
The coordination number of the central
metal atom or ion in a complex is the
number of dative covalent bonds formed
by the central metal atom or ion in a
complex.
The central metal atom Coordination

Complex
or ion in the complex number
[Ag(NH3)2]+ Ag+ 2
[Cu(NH3)4]2+ Cu2+ 4
[Fe(CN)6]3 Fe3+ 6
139
4. Nomenclature of Transition Metal
Complexes with Monodentate Ligands
IUPAC conventions
1. (a) For any ionic compound
the cation is named before
the anion
(b) If the complex is neutral
the name of the complex is
the name of the compound
140
1. (c) In naming a complex (which may be
neutral, a cation or an anion)
the ligands are named before
the central metal atom or ion
the liqands are named in
alphabetical order (prefixes not
counted)
(d) The number of each type of
ligands are specified by the Greek
prefixes
1 mono- 2 di 3 tri
141
4 tetra- 5 penta- 6 hexa-
1. (e) The oxidation number of the
metal ion in the complex is
indicated immediately after the
name of the metal using Roman
numerals
K3[Fe(CN)6]
potassium hexacyanoferrate(III)
[CrCl2(H2O)4]Cl
tetraaquadichlorochromium(III) chloride
[CoCl3(NH3)3]
triamminetrichlorocobalt(III)
142
2. (a) The root names of anionic ligands
always end in -o
CN cyano OH
Cl chloro hydroxo
Br NO2 nitro
bromo SO42
I iodo sulphato
(b) The names of neutral ligands
H
hydrido
are the names of the molecules
except NH3, H2O, CO and
143 NO
Neutral ligand Name of ligand
Ammonia (NH3) Ammine
Water (H2O) Aqua
Carbon monoxide (CO) Carbonyl
Nitrogen monoxide (NO) Nitrosyl
144
3. (a) If the complex is anionic
the suffix -ate is added to
the end of the name of the
metal,
followed by the oxidation
number of that metal
Formula Name of the complex
[CoCl4]2 tetrachlorocobaltate(II) ion
[Fe(CN)6]3 hexacyanoferrate(III) ion
[CuCl4]2 tetrachlorocuprate(II) ion

145
Names of some common metals in anionic complexes
Metal Name in anionic complex
Titanium Titanate
Vanadium Vanadate
Chromium Chromate
Manganese Manganate
Iron Ferrate
Cobalt Cobaltate
Nickel Nickelate
Copper Cuprate
Zinc Zincate
146 Platinum Platinate
3. (b) If the complex is cationic or
neutral
the name of the metal is
unchanged
followed by the oxidation
Formula Name of the complex
number of that metal
[CrCl2(H2O)4]+ tetraaquadichlorochromium(III) ion
[CoCl3(NH3)3] triamminetrichlorocobalt(III)
147
(a) Write the names of the following
compounds.
(i) [Fe(H2O)6]Cl2
(ii) [Cu(NH3)4]Cl2
(iii) [PtCl4(NH3)2]
(iv) K2[CoCl4]
(v) [Cr(NH3)4SO4]NO3
(vi) [Co(H2O)2(NH3)3Cl]Cl
148
(vii) K3[AlF6]
(i) [Fe(H2O)6]Cl2
Hexaaquairon(II) chloride
(ii) [Cu(NH3)4]Cl2
Tetraamminecopper(II) chloride
(iii) [PtCl4(NH3)2]
Diamminetetrachloroplatinum(IV)
(iv) K2[CoCl4]
Potassium tetrachlorocobaltate(II)
(v) [Cr(NH3)4SO4]NO3
Tetraamminesulphatochromium(III) nitrate
149
(a) (vi) [Co(H2O)2(NH3)3Cl]Cl
triamminediaquachlorocobalt(II) chloride
(vii) K3[AlF6]
potassium hexafluoroaluminate
Al has a fixed oxidation state (+3)
no need to indicate the oxidation state
150
(b) Write the formulae of the following
compounds.
(i) pentaamminechlorocobalt(III)
[Co(NH ) Cl]Cl chloride
3 5 2
(ii)Ammonium
(NH ) [TiCl ] hexachlorotitanate(IV)
4 2 6
(iii) Tetraaquadihydroxoiron(II)
[Fe(H2O)4(OH)2]
151
Stereo-structures of complexes
Coordination number
of the central metal Shape of complex Example
atom or ion
sp hybridized
[Ag(NH3)2]+
2
[Ag(CN)2]
linear
152
Coordination number
atom or ion
sp3
[Zn(NH3)4]2+
[CoCl4]2+
Tetrahedral
4
dsp2
[Cu(NH3)4]2+
[CuCl4]2
Square planar
153
Tetra-coordinated Complexes
(a) Tetrahedral complexes [Co(H2O)6]2+
tetrahedral shape Octahedral, pink
154 blue
(b) Square planar complexes
have a square planar structure
155
Example:
156
Coordination number
atom or ion
sp3d2
[Cr(NH3)6]3+
6
[Fe(CN)6]3
Octahedral
157
Hexa-coordinated Complexes
Example:
158
6. Displacement of Ligands and Relative
Stability of Complex Ions
Different ligands have different

tendencies to bind with the metal atom/ion
ligands compete with one another for
the metal atom/ion.
A stronger ligand can displace a weaker
ligand from a complex.
159
6. Displacement of Ligands and Relative
Stability of Complex Ions
Stronger ligand
[Fe(H2O)6]2+(aq) + 6CN(aq)
Hexaaquairon(II) ion
Weaker ligand
[Fe(CN)6]4(aq) + 6H2O(l)
Hexacyanoferrate(II) ion
Reversible reaction Kst 1024 mol6 dm18
Equilibrium position lies to the right
160
Stronger ligand
[Ni(H2O)6]2+(aq) + 6NH3(aq)
Hexaaquanickel(II) ion
Weaker ligand
[Ni(NH3)6]2+(aq) + 6H2O(l)
Hexaamminenickel(II) ion
The greater the equilibrium constant,

the stronger is the ligand on the LHS and
the more stable is the complex on the RHS
The equilibrium constant is called the

stability constant, Kst
161
Spectrochemical Series
A partial spectrochemical series
listing of ligands from small to
large is given below.
I < Br < S2 < SCN < Cl < NO3 < N3
< F < OH < C2O42 H2O < NCS <
CH3CN < py (pyridine) < NH3 < en
(ethylenediamine) < bipy (2,2'-
bipyridine) < phen (1,10-
phenanthroline) < NO2 < PPh3 < CN
CO
162
Consider the general equilibrium system below,
[M(H2O)x]m+ + xLn [M(L)x](m-xn)+ + xH2O
[[M(L)x ] ]
(m xn)
Kst Units = (mol dm3)-x
[[M(H2O)x ] ][L ]
m n x
Kst measures the stability of the complex, [M(L)x](m-xn)+,

relative to the aqua complex, [M(H2O)x]m+
163
monodentate
bidentate
multidentate
Relative strength of some ligands

TAS Expt 6 bonding with copper(II) ions
164
Equilibrium Kst ((mol dm3)n)
[Cu(H2O)4]2+(aq) + 4Cl(aq) 4.2 105
[CuCl4]2(aq) + 4H2O(l)
[Cu(H2O)4]2+(aq) + 4NH3(aq) 1.1 1013
[Cu(NH3)4]2+(aq) + 4H2O(l)
1.0 1018.7
[Cu(H2O)4]2+(aq) + 2H2NCH2CH2NH2(aq)
[Cu(H2NCH2CH2NH2)2]2+(aq) + 4H2O(l)
1.0 1018.8
[Cu(H2O)4]2+(aq) + EDTA4(aq)
[CuEDTA]2(aq) + 4H2O(l)
What is the Kst of the formation of [Cu(H2O)4]2+(aq) ?
165
[Cu(H2O)4]2+ + 4H2O [Cu(H2O)4]2+ + 4H2O
[[Cu(H2O)4 ]2 ]
Kst 1
[[Cu(H2O)4 ] ]
2
166
Factors affecting the stability of complexes
1. The charge density of the central ion

Equilibrium Kst (mol6 dm18)
[Co(H2O)6]2+(aq) + 6NH3(aq) 7.7 104
[Co(NH3)6]2+(aq) + 6H2O(l)
[Co(H2O)6] (aq) + 6NH3(aq)
3+ 4.5 1033
[Co(NH3)6]3+(aq) + 6H2O(l)
[Fe(H2O)6]2+(aq) + 6CN(aq) 1024
[Fe(CN)6]4(aq) + 6H2O(l)
[Fe(H2O)6]3+(aq) + 6CN(aq) 1031
[Fe(CN)6]3(aq) + 6H2O(l)
167
2. The nature of ligands
Ability to form complex : -

CN > NH3 > Cl > H2O
[Zn(CN)4]2Kst = 5 1016 mol4 dm12

[Zn(NH3)4]2+ Kst = 3.8 109 mol4 dm12
[Cu(NH3)4]2+ Kst = 1.1 1013 mol4 dm12

[CuCl4]2+ Kst = 4.2 105 mol4 dm12
168
3. The pH of the solution

In acidic solution, the ligands are protonated
lone pairs are not available
the complex decomposes
[Cu(NH3)4]2+(aq) + 4H2O(l) [Cu(H2O)4]2+(aq) + 4NH3(aq)

H+(aq)
Equilibrium position shifts to the right NH +(aq)
4
169
Consider the stability constants of the following silver
complexes:
Ag+(aq) + 2Cl(aq) [AgCl2](aq)
Kst = 1.1 105 mol2 dm6
Ag+(aq) + 2NH3(aq) [Ag(NH3)2]+(aq)
Kst = 1.6 107 mol2 dm6
Ag+(aq) + 2CN(aq) [Ag(CN)2](aq)
Kst = 1.0 1021 mol2 dm6
What will be formed when CN(aq) is added to a
solution of [Ag(NH3)2]+?
[Ag(CN)2](aq) and NH3
170
Consider the stability constants of the following silver
complexes:
Ag+(aq) + 2Cl(aq) [AgCl2](aq)
Kst = 1.1 105 mol2 dm6
Ag+(aq) + 2NH3(aq) [Ag(NH3)2]+(aq)
Kst = 1.6 107 mol2 dm6
Ag+(aq) + 2CN(aq) [Ag(CN)2](aq)
Kst = 1.0 1021 mol2 dm6
What will be formed when NH3(aq) is added to
a solution of [Ag(CN)2]?
No apparent reaction
171
FeSO4(aq) is used as the antidote for cyanide poisoning
[Fe(H2O)6]2+(aq) + 6CN(aq) [Fe(CN)6]4 + 6H2O(l)
Kst 1 1024 mol6 dm18 Very stable

Only free CN is poisonous
Why is Fe2(SO4)3(aq) not used as the antidote ?
Fe3+(aq) is too acidic.

[Fe(H2O)6]3+(aq) + H2O(l)
[Fe(H2O)5OH]2+(aq) + H3O+(aq)
172
[Cu(H2O)4]2+(aq) + Cl(aq) [Cu(H2O)3Cl]+(aq) + H2O(l)
K1 = 6.3102 mol1 dm3
[Cu(H2O)3Cl]+(aq) + Cl(aq) [Cu(H2O)2Cl2](aq) + H2O(l)

K2 = 40 mol1 dm3
[Cu(H2O)2Cl2](aq) + Cl(aq) [Cu(H2O)Cl3](aq) + H2O(l)

K3 = 5.4 mol1 dm3
[Cu(H2O)Cl3](aq) + Cl(aq) [CuCl4]2(aq) + H2O(l)

K1 = 3.1 mol1 dm3
[Cu(H2O)4]2+(aq) + 4Cl(aq) [CuCl4]2(aq) + 4H2O(l)

Kst = K1 K2 K3 K4 = 4.2 105 mol4 dm12
173
K1 > K2 > K3 > K4
Reasons :
1. Statistical effect
On successive displacement, less water
ligands are available to be displaced.
174
K1 > K2 > K3 > K4
Reasons :
2. Charge effect
On successive displacement, the Cl
experiences more repulsion from the
complex
[Cu(H2O)4]2+ Cl attraction
[Cu(H2O)Cl3] Cl repulsion
175
Colours of some copper(II) complexes
Colour of the
Formula of copper(II) complex
complex
[Cu(H2O)4]2+ Pale blue
[CuCl4]2 Yellow
[Cu(NH3)4]2+ Deep blue

Violet
[Cu(H2NCH2CH2NH2)] 2+
Sky blue
[Cu(EDTA)] 2
The displacement of ligands are usually

accompanied with easily observable colour changes
176
Coloured Ions
The colours of many gemstones are due to the

presence of small quantities of d-block metal ions
177
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 ?
3d10 : Zn2+, Cu+; 3d0 : Sc3+, Ti4+
178
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
179
Cu2+ Blue
Number of unpaired
electrons in 3d
orbitals
V3+ Green
2
Ni2+ Green
V2+ Violet
3 Cr3+ Green
Co2+ Pink
180
Number of unpaired
electrons in 3d
orbitals
Cr2+ Blue
4 Mn3+ Violet
Fe2+ Green
Mn2+ Very pale pink
5
Fe3+ Yellow
181
Co2+(aq) Zn2+(aq) Fe3+(aq)
182
Mn2+(aq) Fe2+(aq) Cu2+(aq)
183
A substance absorbs visible light of a certain
wavelength
reflects or transmits visible light of
other wavelengths (complimentary
colour)
appears coloured
Light Light reflected or
Coloured ion
absorbed transmitted
[Cu(H2O)4]2+(aq) Yellow Blue
[CuCl4]2(aq) Blue Yellow
184
Complimentary colour Violet
chart
Blue light absorbed Blue Magenta
Appears yellow
Cyan Red
Green Yellow
Yellow light absorbed
Appears blue Greenish yellow
185
Coloured Ions
The absorption of visible light is due to the
d-d electronic transition
3d 3d
i.e. an electron jumping from a lower 3d
orbital to a higher 3d orbital
186
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
187
distributes along x and y axes
distributes along z axis
Interact more strongly with d z 2 , d x2 y 2
the orbitals of ligands
eg
d xy , d xz , d yz
t 2g
The splitting of the degenerate 3d orbitals of
a d-block metal ion in an octahedral complex
188
d x 2 y 2
189
Higher energy eg
Criterion for d-d transition : -
presence of unpaired d electrons in the d-
block metal atoms or ions
Or presence of incompletely filled d-subshell
d-d transition is possible for 3d1 to 3d9

arrangements
d-d transition is NOT possible for 3d0 & 3d10

arrangements
190
H2O as ligand
Cu2+
3d9 : d-d transition is possible
191
H2O as ligand
Yellow light absorbed,
appears blue

*
Cu2+
192
Fe2+
193
Magenta light absorbed,
appears green

*
Fe2+
194

Zn2+
3d10 : d-d transition NOT possible
195
Sc3+
3d0 : d-d transition NOT possible
196
E
[Fe(H2O)6]2+ green,
E depends on
[Fe(H2O)6]3+ yellow
1. the nature and charge of metal ion
[Cu(H2O)4]2+ blue,
2. the nature of ligand
197 [CuCl4]2 yellow
Coloured Ions
Why does Na+(aq) appear colourless ?
3d0 : d-d transition is NOT possible
2p 3s transition involves absorption
of radiation in the UV region.
198
Catalytic Properties of Transition
Metals and their Compounds
The d-block metals and their compounds
important catalysts in industry and
biological systems
199
The use of some d-block metals and their compounds as
catalysts in industry
d-Block
Catalyst Reaction catalyzed
metal
V2O5 or Contact process
V
vanadate(V) (VO3) 2SO2(g) + O2 (g) 2SO3(g)
Haber process
Fe Fe N2(g) + 3H2(g) 2NH3(g)
200
The use of some d-block metals and their compounds as
catalysts in industry
d-Block
Catalyst Reaction catalyzed
metal
Hardening of vegetable oil
Ni Ni (Manufacture of margarine)
RCH = CH2 + H2 RCH2CH3
Catalytic oxidation of ammonia

Pt Pt (Manufacture of nitric(V) acid)
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(l)
201
The d-block metals and their compounds
exert their catalytic actions in either
heterogeneous catalysis
homogeneous catalysis
202
Generally speaking, the function of a
catalyst
provides an alternative reaction
pathway of lower activation energy
enables the reaction to proceed
faster than the uncatalyzed one
203
1. Heterogeneous Catalysis
The catalyst and reactants

exist in different states
The most common heterogeneous

catalysts
finely divided solids for gaseous
reactions
204
A heterogeneous catalyst provides a

suitable reaction surface for the reactants
to come close together and react.
205
Example:
The synthesis of gaseous ammonia from
nitrogen and hydrogen (i.e. Haber
process)
N2(g) + 3H2(g) 2NH3(g)
206
In the absence of a catalyst

the formation of gaseous ammonia
proceeds at an extremely low rate
The probability of collision of four

gaseous molecules (i.e. one nitrogen and
three hydrogen molecules)
very small
207
The four reactant molecules

collide in proper orientation in order
to form the product
The bond enthalpy of the reactant (N
N),
very large
the reaction has a high activation
energy
208
In the presence of iron as catalyst

the reaction proceeds much faster
provides an alternative reaction
pathway of lower activation energy
209
Fe is a solid
H2, N2 and NH3 are gases
The catalytic action occurs at the interface
between these two states
The metal provides an active reaction
surface for the reaction to occur
210
1. Gaseous nitrogen and hydrogen

molecules
diffuse to the surface of the
catalyst
2. The gaseous reactant molecules

adsorbed (i.e. adhered) on the
surface of the catalyst
211
2. The iron metal

many 3d electrons and low-lying
vacant 3d orbitals
form bonds with the reactant
molecules
adsorb them on its surface
weakens the bonds present in the
reactant molecules
212
2. The free nitrogen and hydrogen atoms

come into contact with each other
readily to react and form the
product
3. The weak interaction between the
product and the iron surface
gaseous ammonia molecules
desorb easily
213
The catalytic mechanism of the formation of
gaseous ammonia from nitrogen and hydrogen
214
215
216
217
218
43.3 Characteristic Properties of the d-Block Elements and their compound
(SB p.162)
Sometimes, the reactants

in aqueous or liquid state
Other example:
The decomposition of hydrogen peroxide
2H2O2(aq) 2H2O(l) + O2(g)
MnO2(s) as the catalyst
219
Energy profiles of the reaction of nitrogen and hydrogen to
form gaseous ammonia in the presence and absence of a
heterogeneous catalyst
220
2. Homogeneous Catalysis
A homogeneous catalyst
the same state as the reactants and
products
the catalyst forms an intermediate
with the reactants in the reaction
changes the reaction mechanism to
an another one with a lower
activation energy
221
In homogeneous catalysis, the ability of

the d-block metals to exhibit variable
oxidation states enables the formation of
the reaction intermediates.
Example:
The reaction between
peroxodisulphate(VI) ions (S2O82) and
iodide ions (I)
222
Peroxodisulphate(VI) ions
oxidize iodide ions to iodine in an
aqueous solution
themselves being reduced to
sulphate(VI) ions
S2O82(aq) + 2I(aq)
2SO42(aq) + I2 (aq)
Eocell 1.51 V
223
The reaction is very slow due to strong
repulsion between like charges.
Iron(III) ions
take part in the reaction by oxidizing
iodide ions to iodine
themselves being reduced to iron(II)
ions
2I(aq) + 2Fe3+(aq)
I2(aq) + 2Fe2+(aq) = +0.23 V
224
Iron(II) ions
subsequently oxidized by
peroxodisulphate(VI) ion
the original iron(III) ions are
regenerated
2Fe2+(aq) + S2O82(aq)
2Fe3+(aq) + 2SO42(aq) = +1.28
V
225
The overall reaction:

2I(aq) + 2Fe3+(aq)
I2(aq) + 2Fe2+(aq) = +0.23 V
2Fe2+(aq) + S2O82(aq)
+) 2Fe3+(aq) + 2SO42(aq) = +1.28 V
S2O82(aq) + 2I(aq)
2SO42(aq) + I2(aq) = +1.51
V Feasible reaction
226
43.3 Characteristic Properties of the d-Block Elements and their compound
(SB p.164)
Iron(III) ions
catalyze the reaction
acting as an intermediate for the
transfer of electrons between
peroxodisulphate(VI) ions and iodide
ions
227
Peroxodisulphate(VI) ions
oxidize Fe2+ to Fe3+
Iodide ions
reduce Fe3+ to Fe2+
228

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The d-Block Elements

2. Because they do not have vacant d-orbitals neither

3. Copper (Z = 29) can exhibit +2 oxidation state

4. Silver (Z = 47) can exhibit +2 oxidation state

5. The very name transition given to the elements of

1. Physical properties vary slightly with atomic

4. Formation of coloured compounds/ions

The building up of electronic configurations

Relative energy levels of orbitals

Physical properties of d-Block elements :

used for construction and making

used to make aircraft and space

2. The atomic radii of the d-block

Variation in atomic radius

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

the effective nuclear charge

Densities (in g cm3) of the s-block elements and

The first ionization enthalpies of the

Going across the first transition series

The first few successive ionization

Unpaired electrons are relatively

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

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

3. Cr has the highest no. of unpaired

It is because the electrons in the

4. Mn has an exceptionally low m.p.

The hardness of a metal depends on

The metallic bonds of the d-block

In general, the s-block elements

2K(s) + 2H2O(l) 2KOH(aq) + H2(g)

2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g)

Ca(s) + 2H2O(l) Ca(OH)2(aq) + H2(g)

Zn(s) + H2O(g) ZnO(s) + H2(g)

3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g)

Ions of d-block metals have higher charge

Charge density : Fe3+ > Fe2+ > Na+

4. less thermally stable e.g. CuCO3 <<

The 3d and 4s electrons are

Sc2O3 Ti2O3 V2O3 Cr2O3 Mn2O3 Fe2O3 Ni2O3 xH2O

Zinc of the oxidation state +2

(b) All elements of the first transition

E.g. MnO4-, Mn2O7

Mn7+ ions do not exist.

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

Major factor [Ar] 3d5 [Ar] 3d4

Fe3+(aq) > Fe2+(aq)

Major factor H ohydration: Zn2+ > Zn+

1. Interconversions of Vanadium(V) species

Vanadium(V) can exist as cation as well as anion

1. Interconversions of Vanadium(V) species

In acidic medium In alkaline medium

1. Interconversions of Vanadium(V) species

In acidic medium In alkaline medium

1. Interconversions of Vanadium(V) species

In acidic medium In alkaline medium

1. Interconversions of Vanadium(V) species

In acidic medium In alkaline medium

orthovanadate(V) ion VO43(aq) + 8H3O+

Draw the structures of VO43, CrO42 and MnO4

Metavanadate(V) ion VO3(aq) + 6H3O+

The reaction is favoured in alkaline solution

The reaction is favoured in acidic solution

2. The action of zinc powder and