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The d-Block Elements

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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
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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

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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
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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

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Introduction

Cu 3d
+ 10

not transitional
Cu
Cu2+
3d 9

transitional

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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
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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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Characteristics of transition elements

4. Formation of coloured compounds/ions


(cf. colourless ions of s-block elements)

5. Formation of complexes
6. Catalytic properties

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Electronic Configurations

The building up of electronic configurations


of elements follow:
Aufbau principle
Hunds rule
Pauli exclusion principle

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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

18
Cu Cu2+

Relative energy levels of orbitals


in atom and in ion

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Electronic Configurations
Valence electrons in the inner 3d orbitals

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

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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

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

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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
24
d -Block Elements as Metals
d-block elements
extremely useful as construction
materials
strong and unreactive

25
d -Block Elements as Metals
Iron

used for construction and making


machinery nowadays
abundant
cheap
easy to extract

26
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

28
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

29
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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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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Atomic Radii and Ionic Radii

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)

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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

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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
37
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

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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

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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

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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

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2. Ionization Enthalpy
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

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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

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Sharp across periods 1, 2 and 3
Slight across the transition series

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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

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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,
slight and gradual across the series
are observed.

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Electron has to be removed from
completely filled 3p subshell

3d5 Fe3+

3d5 Mn2+
3d10
3d5 Cr+
d10/s2

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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

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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

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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

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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

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Sc Ti V Cr Mn Fe Co Ni Cu Zn
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)
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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)
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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.
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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.
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3. Melting Points and 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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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

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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

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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)

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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+


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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+

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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

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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

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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

+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

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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

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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
1. Variable Oxidation States of Vanadium and
their Interconversions
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
1. Variable Oxidation States of Vanadium and
their Interconversions
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
1. Variable Oxidation States of Vanadium and
their Interconversions
Compounds with vanadium in its highest
oxidation state (i.e. +5)
strong oxidizing agents

81
1. Variable Oxidation States of Vanadium and
their Interconversions
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
1. Variable Oxidation States of Vanadium and
their Interconversions
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. Variable Oxidation States of Vanadium and
their Interconversions

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
1. Variable Oxidation States of Vanadium and
their Interconversions

1. Interconversions of Vanadium(V) species

OH OH OH
VO2+(aq) V2O5(s) VO3(aq) VO43(aq)
H+ H+ H+
Yellow orange yellow colourless

In acidic medium In alkaline medium


Amphoteric

85
1. Variable Oxidation States of Vanadium and
their Interconversions

1. Interconversions of Vanadium(V) species

OH OH OH
VO2+(aq) V2O5(s) VO3(aq) VO43(aq)
H+ H+ H+
Yellow orange yellow colourless

In acidic medium In alkaline medium


Amphoteric
Give the equation for the conversion : V2O5 VO2+
V2O5(s) + 2H+(aq) 2VO2+(aq) + H2O(l)
86
1. Variable Oxidation States of Vanadium and
their Interconversions

1. Interconversions of Vanadium(V) species

OH OH OH
VO2+(aq) V2O5(s) VO3(aq) VO43(aq)
H+ H+ H+
Yellow orange yellow colourless

In acidic medium In alkaline medium


Amphoteric
Give the equation for the conversion : V2O5 VO3
V2O5(s) + 2OH(aq) 2VO3(aq) + H2O(l)
87
1. Variable Oxidation States of Vanadium and
their Interconversions

1. Interconversions of Vanadium(V) species

OH OH OH
VO2+(aq) V2O5(s) VO3(aq) VO43(aq)
H+ H+ H+
Yellow orange yellow colourless

In acidic medium In alkaline medium


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
1. Variable Oxidation States of Vanadium and
their Interconversions

2. The action of zinc powder and


concentrated hydrochloric acid
vanadium(V) ions can be reduced
sequentially to vanadium(II) ions

94
1. Variable Oxidation States of Vanadium and
their Interconversions

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
1. Variable Oxidation States of Vanadium and
their Interconversions
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
1. Variable Oxidation States of Vanadium and
their Interconversions

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
1. Variable Oxidation States of Vanadium and
their Interconversions

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
1. Variable Oxidation States of Vanadium and
their Interconversions

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
their Interconversions
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)


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

104
(d) (e)

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

105
2. Variable Oxidation States of Manganese and
their Interconversions
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
Formation of Complexes
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
Formation of Complexes
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
Formation of Complexes
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
What is the oxidation state of the central metal ?

Co3+

130
What is the oxidation state of the central metal ?

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
Stereo-structures of complexes
Coordination number
of the central metal Shape of complex Example
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
Tetra-coordinated Complexes
(b) Square planar complexes
have a square planar structure

155
Tetra-coordinated Complexes

Example:

156
Stereo-structures of complexes
Coordination number
of the central metal Shape of complex Example
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
Factors affecting the stability of complexes

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
Factors affecting the stability of complexes

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
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

180
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

181
Co2+(aq) Zn2+(aq) Fe3+(aq)

Colours of some d-block metal ions in aqueous solutions

182
Mn2+(aq) Fe2+(aq) Cu2+(aq)

Colours of some d-block metal ions in aqueous solutions

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+

3d9 : d-d transition is possible

192
Fe2+

3d6 : d-d transition is possible

193
Magenta light absorbed,
appears green

*
Fe2+

3d6 : d-d transition is possible

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
Catalytic Properties of Transition
Metals and their Compounds
The d-block metals and their compounds
exert their catalytic actions in either
heterogeneous catalysis
homogeneous catalysis

202
Catalytic Properties of Transition
Metals and their Compounds
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
1. Heterogeneous Catalysis

A heterogeneous catalyst provides a


suitable reaction surface for the reactants
to come close together and react.

205
1. Heterogeneous Catalysis

Example:
The synthesis of gaseous ammonia from
nitrogen and hydrogen (i.e. Haber
process)

N2(g) + 3H2(g) 2NH3(g)

206
1. Heterogeneous Catalysis

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
1. Heterogeneous Catalysis

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
1. Heterogeneous Catalysis

In the presence of iron as catalyst


the reaction proceeds much faster
provides an alternative reaction
pathway of lower activation energy

209
1. Heterogeneous Catalysis

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. Heterogeneous Catalysis

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
1. Heterogeneous Catalysis

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
1. Heterogeneous Catalysis

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
The catalytic mechanism of the formation of
gaseous ammonia from nitrogen and hydrogen
215
The catalytic mechanism of the formation of
gaseous ammonia from nitrogen and hydrogen
216
The catalytic mechanism of the formation of
gaseous ammonia from nitrogen and hydrogen
217
The catalytic mechanism of the formation of
gaseous ammonia from nitrogen and hydrogen
218
43.3 Characteristic Properties of the d-Block Elements and their compound
(SB p.162)

1. Heterogeneous Catalysis

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
2. Homogeneous Catalysis

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
2. Homogeneous Catalysis

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
2. Homogeneous Catalysis
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
2. Homogeneous Catalysis

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
2. Homogeneous Catalysis

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)

2. Homogeneous Catalysis

Iron(III) ions
catalyze the reaction
acting as an intermediate for the
transfer of electrons between
peroxodisulphate(VI) ions and iodide
ions

227
2. Homogeneous Catalysis

Peroxodisulphate(VI) ions
oxidize Fe2+ to Fe3+
Iodide ions
reduce Fe3+ to Fe2+

228