The First Transition Series

Chapter 45
The First Transition Series
45.1 Introduction
45.2 General Features of the d-Block Elements
from Sc to Zn
45.3 Characteristic Properties of the d-Block
Elements and their Compounds
1
1 New Way Chemistry for Hong Kong A-Level Book 4
45.1 Introduction (SB p.164)
The first transition series
2
d-Block elements (transition elements):
• Lie between s-block and p-block elements
• Occur in the fourth and subsequent periods
• All contains incomplete d sub-shell (i.e. 1 – 9 electrons) in at

least one of their oxidation state
Titanium
Scandium Chromium
Vanadium
Manganese
Iron Zinc
Cobalt Copper
3 Nickel
New Way Chemistry for Hong Kong A-Level Book 4
3
• Strictly speaking, scandium (Sc) and zinc (Zn) are not

transitions elements
∵ Sc forms Sc3+ ion which has an empty d sub-shell (3d0)
Zn forms Zn2+ ion which has a completely filled d sub-
shell (3d10)
4
• Cu shows some intermediate behaviour between transition

and non-transition elements because of two oxidation states,
Cu(I) & Cu(II)
• Cu+ is not a transition

metal ion as it has a
completely filled d sub-
shell
• Cu2+ is a transition metal
ion as it has an
incompletely filled
d sub-shell
5
45.2 General Features of the d-Block Elements from Sc to Zn (SB p.165)
Electronic Configurations
Relative energy levels of orbitals before

and after filling with electrons
6
• Before filling electrons, the energy of 4s sub-shell is

lower than that of 3d sub-shell
⇒ 4s sub-shell is filled before 3d sub-shell
• Once the 4s sub-shell is filled, the energy will increase
⇒ The lowest energy sub-shell becomes 3d sub-shell, so

the next electron is put into 3d sub-shell
7
Electronic configurations of the first series of d-block elements
Atomic Electronic
Element
number configuration
Scandium 21 [Ar]3d14s2
Titanium 22 [Ar]3d24s2
Vanadium 23 [Ar]3d34s2
Chromium 24 [Ar]3d54s1
Manganese 25 [Ar]3d54s2
Iron 26 [Ar]3d64s2
Cobalt 27 [Ar]3d74s2
Nickel 28 [Ar]3d84s2
Copper 29 [Ar]3d104s1
Zinc 30 [Ar]3d104s2 8
• Cr is expected to be [Ar] 3d44s2 but the actual

configuration is [Ar] 3d54s1
• Cu has the electronic configuration of [Ar] 3d104s1
instead of [Ar] 3d94s2
• This can be explained by the fact that a half-filled or

fully-filled d sub-shell provides extra stability
9
d-Block Elements as Metals
• d-block elements are typical metals

(1) good conductors of heat and electricity, hard,
strong, malleable, ductile and lustrous
(2) high melting and boiling points except Hg is a liquid
at room temperture
• These properties make d-block elements as good
construction materials
e.g. Fe is used for construction and making machinery
Ti is used to make aircraft and space shuttles
10
• Transition elements have similar atomic radii which

make them possible for the atom of one element to
replace those of another element in the formation of
alloy
e.g. Mn is for conferring hardness and wearing resistance

to its alloy (duralumin)
Cr is for conferring inertness on stainless steel
11
Iron is used to make ships Tsing Ma Bridge is

constructed of steel
12
Tungsten in a light bulb
The statue is made of alloy of copper and zinc
Titanium is used in making aircraft Jewellery made of gold

13
Atomic Radii and Ionic Radii

Observations:
• d-block metals have smaller
atomic radii than s-block
metals
• The atomic radii of the d-
block metals do not show
much variation across the
series
• The atomic radii decrease
initially, remain almost
constant in the middle and
then increase at the end of
series
14
Variations in atomic and ionic radii of

the first series of d-block elements
15
• The atomic size reduces at the beginning of the series

∵ increase in effective nuclear charge with atomic numbers
⇒ the electron clouds are pulled closer to the nucleus
⇒ causing a reduction in atomic size
• The atomic size decreases slowly in the middle of the series

∵ when more and more electrons enter the inner 3d sub-shell
⇒ the screening and repulsive effects of the electrons in the
3d sub-shell increase
⇒ the effective nuclear charge increases slowly
16
• The atomic size increases at the end of the series
∵ the screening and repulsive effects of the 3d

electrons reach a maximum
• The reasons for the trend of the ionic radii of the d-block
elements are similar to those for the atomic radii.
• Remember that the electrons have to be removed from the

4s orbital first
17
Comparison of Some Physical and Chemical

Properties between d-Block and s-Block Metals
Density
Densities (in g cm-3) of the s-block metals

and the first series of d-block metals
18
• d-block metals are generally denser than the s-block

because most of the d-block metals have close-packed
structures while most of the s-block metals do not.
• The densities increase generally across the first series of

d-block metals. This is in agreement with the general
decrease in atomic radius across the series
19
Ionization Enthalpy
Ionization enthalpy (kJ mol–1)
Element
1st 2nd 3rd 4th
K 418 3 070 4 600 5 860
Ca 590 1 150 4 940 6 480
Sc 632 1 240 2 390 7 110
Ti 661 1 310 2 720 4 170
V 648 1 370 2 870 4 600
Cr 653 1 590 2 990 4 770
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 20
• 1st I.E. of d-block metals are greater than those of s-block

elements in the same row of the Periodic Table.
∵ the d-block metals are smaller in size than the s-block

metals, thus they have greater effective nuclear charges
• For K, the 2nd I.E. is exceptionally higher than its 1st I.E
• For Ca, the 3rd I.E. is exceptionally higher than its 2nd I.E
∵ the electrons are come form the inner fully-filled electron

shells
21
• The first few successive I.E. for d-block elements do not

show dramatic changes
∵ removal of electrons does not involve the disruption
of inner electron shells
• The 1st I.E. of the d-block metals increase slightly and
irregularly across the series
∵ Going across the first transition series, the nuclear charge

of the elements increases, and additional electrons are
found in the inner 3d sub-shell
⇒ The additional screening effect of the additional 3d

electrons is so significant that the effective nuclear charge of
the elements increases only very slowly across the series
22
• Successive ionization enthalpies exhibit a similar

gradual increase across the first transition series
• The increases in the 3rd and 4th ionization enthalpies

across the series are progressively more rapid
23
• Some abnormal
high ionization
enthalpy, e.g. 1st I.E.
of Zn, 2nd I.E. of Cr
& Cu and the 3rd I.E.
of Mn
∵The removal of an
electron from a fully-
filled or half-filled
sub-shell requires a
relatively large
amount of energy
Variation of successive ionization enthalpies of
the first series of the d-block elements
24
Check Point 45-1

Explain the following variation in terms of electronic
configurations.
(a) The second ionization enthalpies of both Cr and Cu are
higher (a)
than
Thethose
secondof their next
ionization elements
enthalpies respectively.
of both Cr and Cu are higher
than those of their next elements respectively. In the case of Cr,Answer
the
second ionization enthalpy involves the removal of an electron from a
half-filled 3d sub-shell, which has extra stability. Therefore, this second
ionization enthalpy is relatively high. The case is similar for copper where
its second ionization enthalpy involves the removal of an electron from a
fully-filled 3d sub-shell which also has extra stability. Thus, its
second ionization enthalpy is also relatively high.
25
Check Point 45-1 (cont’d)

Explain the following variation in terms of electronic
configurations.
(b) The third ionization enthalpy of Mn is higher than that of
its next element.
Answer
(b) The third ionization enthalpy of Mn is higher than that

of its next element. It is because its third ionization
enthalpy involves the removal of an electron from a half-
filled 3d sub-shell which has extra stability. Therefore, its
third ionization enthalpy is relatively high.
26
Electronegativity
Electronegativity values of the s-block metals

and the first series of the d-block metals
27
• The electronegativity of d-block metals are generally

higher than those of the s-block metals
∵ Generally, d-block metals have smaller atomic radii

than s-block metals
⇒ the nuclei of d-block metals can attract the electrons
in a bond more tightly towards themselves
28
• The electronegativity shows a slight increase generally

with increasing atomic numbers across the series
∵ Gradual increase in effective nuclear charge and

decrease in atomic radius across the series
⇒ The closer the electron shell to the nucleus, the more

strongly the additional electron in a bond is
attracted
⇒ Higher electronegativity
29
Melting Point and Hardness
Melting points (°C) of the s-block metals and

the first series of the d-block metals
30
• The melting points of the d-block metals are much higher

than those of the s-block metals
Reasons:
1. d-block metal atoms are small in size and closely packed in

the metallic lattice. All Group I metals and some Group II
metals do not have close-packed structures
2. Both 3d and 4s electrons of d-block metals participate in

metallic bonding by delocalizing into the electron sea, and
thus the metallic bond strength is very strong
s-Block metals have only 1 to 2 valence electrons per atom
delocalizing into the electron sea
31
• The hardness of a metal depends on the strength of the

metallic bonds
∵ The metallic bond of d-block metals is stronger

than that of s-block metals
⇒ d-block metals are much harder than the s-block

metals
32
Check Point 45-2

What are the differences between the structures and bonding
of the d-block and s-block metals? How do these differences
affect their melting points?
The d-block metals are comparatively small, and the metallic atoms
are closely packed in the metallic lattice. Besides, both the 3d and 4s
electrons of the d-block metals participate in metallic bonding Answer
by
delocalizing into the electron sea. The strength of metallic bond in these
metals is thus very strong. In the case of s-block metals, the metallic
radius is larger and most of them do not have close-packed structures.
Also , as they have only one or two valence electrons per atom
delocalizing into the electron sea, the metallic bond formed is
weaker. Therefore, the d-block metals have a much higher
melting point than the s-block metals.
33
Reaction with Water
• Generally, s-block metals (e.g. K, Na & Ca) react with

H2O vigorously to form metal hydroxides and H2
• d-block metals react only very slowly with cold water.

Zn and Fe are relatively more reactive
⇒ Zn and Fe react with steam to give metal oxides

and H2
Zn(s) + H2O(g) → ZnO(s) + H2(g)
3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g)

34
Elements and their Compounds (SB p.175)
Variable Oxidation States
• d-block elements has ability to show variable oxidation

states
∵ 3d & 4s electrons are of similar energy levels, the
electrons in both of them are available for bonding
⇒ When the first transition elements react to form
compounds, they can form ions of roughly the same
stability by losing different numbers of electrons
⇒ Form compounds with a wide variety of oxidation
states
35
Oxidation states of the elements of the first
transition series in their oxides and chlorides
Oxidation
Oxide/Chloride
state
Cu2O
+1
Cu2Cl2
TiO VO CrO MnO FeO 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
36
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
37
Observations:
1. Sc and Zn do not exhibit variable oxidation states. Sc3+ has

electronic configuration of argon (i.e. 1s22s22p63s23p6). Zn2+
has the electronic configuration of [Ar] 3d10. Other oxidation
states are not possible.
2. Except Sc, all elements have +2 oxidation state. Except Zn,

all elements have +3 oxidation state
3. The highest oxidation state is +7 at Mn. This corresponds to

removal of all 3d & 4s electrons. (Note: max.oxidation state is
NEVER greater than the total number of 3d & 4s electrons)
38
4. There is a reduction in the number of oxidation states after

Mn.
∵ decrease in the number of unpaired electrons and
increase in nuclear charge which holds the 3d electrons
more firmly
5. The relative stability of various oxidation states can be

correlated -with the stability of empty, half-filled and fully-
filled configuration
e.g. Ti4+ is more stable than Ti3+ (∵ [Ar]3d0 configuration)

Mn2+ is more stable than Mn3+ (∵ [Ar]3d5 configuration)
Zn2+ is more stable than Zn+ (∵ [Ar]3d10 configuration) 39
Variable Oxidation States of Vanadium and their

Interconversions
• Vanadium shows oxidation states from +2 to +5 in its
compounds
• In these oxidation state, vanadium forms ions which
have distinctive colours in aqueous solutions
Ion Oxidation state Colour

V2+ +2 Violet
V3+ +3 Green
VO2+ +4 Blue
VO2+ +5 Yellow
40
• In acidic medium, vanadium(V) state occurs as VO2+(aq);

vanadium(IV) state occurs as VO2+(aq)
• In alkaline medium, vanadium(V) state occurs as VO3–(aq)
• Most compounds with vanadium(V) are good oxidizing agents
while those with vanadium(II) are good reducing agents
• The starting material for the interconversions of
common oxidation states of vanadium is ammonium
vanadate(V) (NH4VO3)
• When NH4VO3 is acidified, vanadium exists in the form

of VO2+(aq) which the oxidation state of +5
41
• Vanadium(V) ions can be reduced sequentially to
vanadium(II) ions by the action of Zn powder and acid
• The sequence of colour changes forms a characteristic
test for vanadium
Zn Zn Zn
VO2 (aq) →
+
conc. HCl
VO (aq)
2+
→
conc. HCl
V (aq) → 3+
conc. HCl
V2+
(aq)
yellow blue green violet
42
• The feasibility of the changes in oxidation number of

vanadium can be predicted by using electrode potentials
easily
Half reaction E (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
43
• Under standard conditions, Zn can reduce vanadium(V) to

vanadium(IV) as the Ecell value is +ve
2 × (VO2+(aq) + 2H+(aq) + e– VO2+(aq) + H2O(l)) E = +1.00 V
–) Zn2+(aq) + 2e– Zn(s) E = –0.76 V
2VO2+(aq) + Zn(s) + 4H+(aq)
2VO2+(aq) + Zn2+(aq) + 2H2O(l) Ecell = +1.76 V
44
• Further reduction of vanadium(IV) to vanadium(III) by Zn is

feasible as the Ecell value is +ve
2 × (VO2+(aq) + 2H+(aq) + e– V3+(aq) + H2O(l)) E = +0.34 V
–) Zn2+(aq) + 2e– Zn(s) E = –0.76 V
2VO2+(aq) + Zn(s) + 4H+(aq)
2V3+(aq) + Zn2+(aq)+ 2H2O(l) Ecell = +1.10 V
45
• Further reduction of vanadium(III) to vanadium(II) by Zn is

also feasible
2 × (V3+(aq) + e– V2+(aq)) E = +0.34 V
–) Zn2+(aq) + 2e– Zn(s) E = –0.76 V
2V3+(aq) + Zn(s) 2V2+(aq) + Zn2+(aq) Ecell = +0.50 V
Conclusion:
Zn acts as a strong reducing agent which reduces vanadium(V)
through vanadium(IV), vanadium(III) and finally to
vanadium(II) in an acidic medium
46
Variable Oxidation States of Manganese and their
Interconversions
• Mn shows oxidation states from +2 to +7 in its compounds
• The most common oxidation states of Mn include +2, +4, +7
• Mn also forms coloured compounds or ions in these
oxidation states
Ion/compound Oxidation state Colour

Mn2+ +2 Very pale pink
Mn(OH)3 +3 Dark brown
MnO2 +4 Black
MnO42– +6 Green
MnO4– +7 Purple
47
• Mn is most stable in +2 oxidation state

• The most common Mn compound in +4 oxidation state is
MnO2 which is a strong oxidizing agent. It reacts with
reducing agents and is reduced to Mn2+
+4
MnO
black 2(s) + 4H+
(aq) + 2e–
+2
Mnpale(aq)
very
2+
pink + 2H2O(l) E = +1.23 V
• MnO2 is used in the laboratory production of chlorine
MnO2(s) + 4HCl(aq) → MnCl2(aq) + 2H2O(l) + Cl2(g)

48
• The most common Mn compound in +7 oxidation state is

KMnO4 which is an extremely powerful oxidizing agent. Its
oxidizing power depends on pH
• In acidic medium, MnO4– ions are reduced to Mn2+ ions
+7 +2
MnO
purple
4
–
(aq) + 8H+
(aq) + 5e –
Mn 2+
(aq)
very pale pink + 4H2O(l)
E = +1.23 V
• In alkaline medium, MnO4– ions are reduced to MnO2

+7 +4
MnO 4
purple
–
(aq) + 2H2 O(l) + 3e –
MnO
black2 (s) + 4OH–
(aq)
E = +0.59 V
49
Mn(II) Mn(IV) Mn(VII)
Mn(III) Mn(VI)
50
Check Point 45-3

(a) The oxidation numbers of copper in its compounds are +1
and +2.
(i) Give the names, formulae and colours of compounds
formed between copper and oxygen.
(ii) Is copper more stable in the oxidation state of +1 or
+2? Answer
(a) (i) Copper(I) oxide Cu2O – reddish brown
Copper(II) oxide CuO – black
(ii) +2
51

(b) Explain the following:
(i) When iron(II) sulphate(VI) (FeSO4) is required, it has
to be freshly prepared.
(ii) When aluminium reacts with chlorine and hydrogen
chloride respectively, aluminium chloride (AlCl3) is
(b) (i) Iron(II) sulphate(VI) solution cannot be stored for a long time. It
formed in both cases. However, two different products
will be oxidized by air to form iron(III) sulphate(VI).
are produced when iron reacts with these two
(ii) Aluminium has only one oxidation state (+3) in its compounds,
chemicals respectively.
whereas iron has two (+2 & +3). Iron reacts with the oxidizing
Answer
agent Cl2 to form FeCl3 but with the non-oxidizing agent
HCl to give FeCl2.
52
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 form the dative covalent bonds

are called ligands
• In a ligand, there is at least one atom having a lone pair of

electrons which can be donated to the central metal atom or
ion to form a dative covalent bond
53
Examples of ligands:
54
• Depending on the overall charge of the complex formed,

complexes are classified into 3 main types: cationic, neutral
and anionic complex
Cationic complex ions

55
Neutral complex
Anionic
complex ions
56
• The coordination number of the central metal atom or ion

in a complex is the number of ligands bonded to this metal
atom or ion
e.g. in [Cu(NH3)4]2+(aq), there are 4 ligands are bonded to

the central Cu2+ ion, so the coordination number is 4
• The most common coordination numbers are 4 and 6
57
• For the first series of d-block metals, complexes are formed

using the 3d, 4s, 4p and 4d orbitals present in the metal
atoms or ions
• Due to the presence of vacant, low energy orbitals, d-block

metals can interact with the orbitals of the surrounding
ligands
• Due to the the relatively small sizes and high charge of

d-block metal ions, they introduce strong polarization on the
ligands. This favours the formation of bonds of high
covalent character
58
Diagrammatic representation of the formation of a complex

59
Nomenclature of Complexes
• Complexes are named according to the rules recommended
by IUPAC
The rules of naming a complex are as follow:
1. (a) For any ionic compound, the cation is named before the
anion.
(b) If the compound is neutral, then the name of the complex
is name of the compound
(c) In naming a complex, the ligands are named before the
central metal atom or ion, negative ones first
and then neutral ones
60
(d) The number of each type of ligands are specified by the

Greek prefixes: mono-, di-, tri-, tetra-, penta-, hexa-, etc.
(e) The oxidation number of the metal ion in the complex is

named immediately after it by Roman numerals
Therefore,
K3[Fe(CN)6] potassium hexacyanoferrate(III)
[CrCl2(H2O)4]Cl dichlorotetraaquachromium(III) chloride
[CoCl3(NH3)] trichlorotriamminecobalt(III)
Note: in the formulae, the complexes are always enclosed in [ ]

61
2. (a) The root names of anionic ligands always end in -o.
e.g. CN– cyano
Cl– chloro
(b) The names of neutral ligands are the names of the
molecules, except NH3, H2O, CO and NO
e.g. NH3 ammine
H2O aqua
Name of Name of
Anionic ligand Neutral ligand
ligand ligand
Bromide (Br–)
Chloride (Cl–) Bromo Ammonia (NH3) Ammine
Cyanide (CN–) Chloro Water (H2O) Aqua
Fluoride (F–) Cyano Carbon monoxide Cabonyl
Hydroxide (OH–) Fluoro (CO) Nitrosyl
Sulphate(VI) Hydroxo Nitric oxide (NO)
(SO42–) Sulphato
62
62 Amide (NH2–) New WayAmido
Chemistry for Hong Kong A-Level Book 4
3. (a) If the complex is anionic, then the suffix -ate is

attached to the name of the metal, followed by the
oxidation state of that metal
e.g. K2CoCl4 potassium tetrachlorocobaltate(II)

K3Fe(CN)6 potassium hexacyanoferrate(III)
[CuCl4]2– tetrachlorocuprate(II) ion
63
Metal Name in anionic complex
Titanium Titanate
Chromium Chromate
Manganese Manganate
Iron Ferrate
Cobalt Cobaltate
Nickel Nickelate
Copper Cuprate
Zinc Zincate
Platinum Platinate
(b) If the complex is cationic or neutral, then the name of the
metal is unchanged.
e.g. [CrCl2(H2O)4]+ dichlorotetraaquachromium(III) ion
[CoCl3(NH3)3] trichlorotriamminecobalt(III)
64
Examples:
1. Ionic complexes
65
2. Neutral complex
66
Check Point 45-4

(a) Name the following compounds.
(i) [Fe(H2O)6]Cl2
(ii) [Cu(NH3)4]Cl2
(iii) [PtCl4(NH3)2]
(iv) K2[CoCl ] Hexaaquairon(II) chloride
(a) 4(i) Answer
(ii) Tetraamminecopper(II) chloride
(iii) Tetrachlorodiammineplatinum(IV)
(iv) Potassium tetrachlorocobaltate(II)
67

(b) Write the formulae of the following compounds.
(i) chloropentaamminecobalt(III) chloride
(ii) ammonium hexachlorotitanate(IV)
(iii) dihydroxotetraaquairon(II)
Answer
(b) (i) [CoCl(NH3)5]Cl2
(ii) (NH4)2[TiCl6]
(iii) [Fe(H2O)4(OH)2]
68
Displacement of Ligands and Relative Stability

of Complex Ions
• The tendency to donate unshared electrons to form dative

covalent bonds varies with different ligands
• Different ligands form dative covalent bonds of different

strength with the metal atom or ion
• The ligand within a complex can be replaced by another

ligand if the incoming ligand can form a stronger bond with
the metal atom or ion
• When different ligands are present, they compete for a metal ion
69
• A stronger ligand (e.g. CN–, Cl–) can displace a weaker

ligand (e.g. H2O) from a complex, and a new complex is
formed
e.g. [Fe(H2O)6]2+(aq) + 6CN–(aq) [Fe(CN)6]4–(aq) + 6H2O(l)
hexaaquairon(II) ion hexacyanoferrate(II) ion
[Ni(H2O)6]2+(aq) + 6NH3(aq) [Ni(NH3)6]2+(aq) + 6H2O(l)

hexaaquanickel(II) ion hexaamminenickel(II) ion
• Complex ions are usually coloured and the colours are

related to the types of ligands present
⇒ Displacement of ligands usually associated with colour
changes which can be followed during experiments easily
70
Example:
• 0.5 M CuSO4 solution is put into a test tube. The complex
ion present is [Cu(H2O)6]2+ which is pale blue
• Conc. HCl is added dropwise to the CuSO4 solution
• The solution turns from pale blue to green and finally to

yellow
• This is due to the stepwise replacement of H2O ligands
by Cl– ligands
• Each stage is charaterized by an equilibrium constant
called the stepwise stability constant 71
[Cu(H2O)4]2+(aq) + Cl–(aq) [Cu(H2O)3Cl]+(aq) + H2O(l)
K1 = 6.3 × 102 dm3 mol–1
[Cu(H2O)3Cl]+(aq) + Cl–(aq) [Cu(H2O)2Cl2](aq) + H2O(l)
K2 = 4.0 × 101 dm3 mol–1
[Cu(H2O)2Cl2](aq) + Cl–(aq) [Cu(H2O)Cl3]–(aq) + H2O(l)
K3 = 5.4 dm3 mol–1

[Cu(H2O)Cl3]–(aq) + Cl–(aq) [CuCl4]2–(aq) + H2O(l)
K4 = 3.1 dm3 mol–1
72
Overall equation:
[Cu(H2O)4]2+(aq) + 4Cl–(aq) [CuCl4]2–(aq) + 4H2O(l)
Overall stability constant of [CuCl4]2–(aq) is:

[[CuCl 4 ]2− (aq )]eqm
K st =
[[Cu(H 2O) 4 ]2+ (aq )]eqm [Cl − (aq)]4 eqm
which is given by:
Kst = K1 × K2 × K3 × K4 = 4.2 × 105 dm12 mol–4
73
• The larger the overall stability constant, the more stable is

the complex
• In this example, the overall equilibrium lies mainly on the right

and [CuCl4]2–(aq) is predominant over [Cu(H2O)4]2+(aq)
⇒ Cl– ligands can replace H2O ligands to form a more stable

complex with Cu2+ ion
74
• The stepwise stability constant decreases from K1 to K4
Reasons:
1. When the central Cu2+ ion is surrounded by an increasing

number of Cl– ligands, the chance for an addition Cl–
ligand to replace a remaining bonded H2O decreases
2. There is a progressive change from a cationic complex to

a neutral complex, and then anionic complex. Due to the
electrostatic repulsion between anionic complex and Cl–
ions, the approach of Cl– ligands becomes more difficult
75
• NH3 forms a more stable complex with Cu2+ ion than Cl–
and H2O ligands do
• NH3 can displace both H2O ligands from [Cu(H2O)4]2+(aq)

and Cl– ligands from [CuCl4]2–(aq), forming the deep blue
[Cu(NH3)4]2+(aq) ion
[Cu(H2O)4]2+(aq) + 4NH3(aq)
[Cu(NH3)4]2+(aq) + 4H2O(l)
76
• The displacement also occurs in stepwise reaction
[Cu(H2O)4]2+(aq) + NH3(aq) [Cu (NH3)(H2O)3]2+(aq) + H2O(l)
K1 = 1.9 × 104 dm3 mol–1
[Cu(NH3)(H2O)3]2+(aq) + NH3(aq) [Cu (NH3)2(H2O)2]2+(aq) + H2O(l)

K2 = 3.9 × 103 dm3 mol–1
[Cu(NH3)2(H2O)2]2+(aq) + NH3(aq) [Cu (NH3)3(H2O)]2+(aq) + H2O(l)

K3 = 1.0 × 103 dm3 mol–1
[Cu(NH3)3(H2O)]2+(aq) + NH3(aq) [Cu (NH3)4]2+(aq) + H2O(l)

K4 = 1.5 × 102 dm3 mol–1
77
• By adding the above 4 equations, overall equation is
obtained.
[Cu(H2O)4]2+(aq) + 4NH3(aq) [Cu(NH3)4]2+(aq) + 4H2O(l)
• Overall stability constant of [Cu(NH3)4]2+(aq) is:

[[Cu(NH3 ) 4 ]2+ (aq)]eqm
K st =
[[Cu(H 2O) 4 ]2+ (aq)]eqm [ NH 3 (aq)]4 eqm
which is given by Kst = K1 × K2 × K3 × K4 = 1.1 × 1013 dm12 mol–4

• The overall stability constant for [Cu(NH3)4]2+(aq) is
larger than that for [CuCl4]2–(aq)
⇒ NH3 is a stronger ligand compared with Cl– or H2O

⇒ [Cu(NH3)4]2+(aq) is more stable than [CuCl4]2–(aq) 78
• The displacement of the H2O ligands in [M(H2O)m] by

another ligand L can be represented as:
[M(H2O)m] + mL [MLm] + mH2O
• The stability constant for the complex [MLm] at a given
temp.: [ML m ]
K st =
[M(H 2 O) m ][ L]m
Kst ((mol dm–3)–
Equilibrium n
)
Cr(OH)3(aq) + OH–(aq) [Cr(OH)4]–(aq) 1 × 10–2
[Fe(H2O)6]2+(aq) + 6CN–(aq) [Fe(CN)6]4–(aq) + 6H2O(l) ≈ 1024
[Fe(H2O)6]3+(aq) + 6CN–(aq) [Fe(CN)6]3–(aq) + 6H2O(l) ≈ 1031
[Fe(H2O)4]3+(aq) + 4Cl–(aq) [FeCl4]–(aq) + 4H2O(l) 8 × 10–2
79
Equilibrium Kst ((mol dm–3)–n)

[Co(H2O)6]2+(aq) + 6NH3(aq) [Co(NH3)6]2+(aq) + 6H2O(l) 7.7 × 104
[Co(H2O)6]3+(aq) + 6NH3(aq) [Co(NH3)6]3+(aq) + 6H2O(l) 4.5 × 1033
[Ni(H2O)6]2+(aq) + 6NH3(aq) [Ni(NH3)6]2+(aq) + 6H2O(l) 4.8 × 107
4.8 × 105
[Cu(H2O)4]2+(aq) + 4Cl– [CuCl4]2–(aq) + 4H2O(l)
[Cu(H2O)4]2+(aq) + NH3(aq)
1.9 × 104 (K1)
[ Cu(NH3)(H2O)3]2+(aq) + H2O(l)
[Cu(NH3)(H2O)3]2+(aq) + NH3(aq)
3.9 × 103 (K2)
[ Cu(NH3)2(H2O)2]2+(aq) + H2O(l)
[Cu(NH3)2(H2O)2]2+(aq) + NH3(aq)
1.0 × 103 (K3)
[ Cu(NH3)3(H2O)]2+(aq) + H2O(l)
[Cu(NH3)3(H2O)]2+(aq) + NH3(aq) 1.5 × 102 (K4)
[ Cu(NH3)4]2+(aq) + H2O(l)
1.1 × 1013
[Cu(H2O)4]2+(aq) + 4NH3(aq) [Cu(NH3)4]2+(aq) + 4H2O(l)
(Kst = K1×K2×K3×K4)
80
Equilibrium Kst ((mol dm–3)–n)

[Zn(H2O)4]2+(aq) + 4CN–(aq) [Zn(CN)4]2– (aq) + 4H2O(l) 5 × 1016
[Zn(H2O)4]2+(aq) + 4NH3(aq) [Zn(NH3)4]2+(aq) + 4H2O(l) 3.8 × 109
Zn(OH)2(s) + 2OH–(aq) [Zn(OH)4]2– (aq) 10
• As shown in the table, the values of stability constants

are very large
⇒ The complex ions of the d-block metals are generally

very stable
81
Check Point 45-5

Answer the following questions by considering the stability
constants of the silver complexes.
Ag+(aq) + 2Cl–(aq) [AgCl2]–(aq) Kst = 1.1 × 105 mol–2 dm6
Ag+(aq) + 2NH3(aq) [Ag(NH3)2]+(aq) Kst = 1.6 × 107 mol–2 dm6
Ag+(aq) + 2CN–(aq) [Ag(CN)2]–(aq) Kst = 1.0 × 1021 mol–2 dm6
(a) Give the most stable and the least stable complexes of
silver. Answer
(a) The most stable complex of silver is
[Ag(CN)2]–(aq), whereas the least stable one
is [AgCl2]–(aq)
82

Answer the following questions by considering the stability
constants of the silver complexes.
Ag+(aq) + 2Cl–(aq) [AgCl2]–(aq) Kst = 1.1 × 105 mol–2 dm6
Ag+(aq) + 2NH3(aq) [Ag(NH3)2]+(aq) Kst = 1.6 × 107 mol–2 dm6
Ag+(aq) + 2CN–(aq) [Ag(CN)2]–(aq) Kst = 1.0 × 1021 mol–2 dm6
(b) (i) What will be formed when CN–(aq) is added to a

solution of [Ag(NH3)2]+?
(ii) What(b)will
(i) be formed
[Ag(CN) – when NH (aq) is added to a
2] (aq) and NH3(aq)
3
solution(ii)
of [Ag(CN)
No reaction2] ?
–
Answer
83
Stereostructures of Tetra- and Hexa-
Coordinated Complexes
• The spatial arrangement of ligands around the central

metal atom or ion in a complex is referred to as the
stereochemistry of the complex
• The coordination number of the central metal atom or ion is
determined by:
1. The size of the central metal atom or ion;
2. The number and the nature of vacant orbitals of the
d-block metal atoms or ions available for the
formation of dative covalent bonds
84
Shape
1. Tetra-coordinated complexes
(a) Tetrahedral complexes
Tetrahedral shape is a common
geometry of tetra-coordinated complexes
Examples:
85
(b) Square planar complexes

Some tetra-coordinated complexes
show a square planar structure
Examples:
86
2. Hexa-coordinated complexes
For complexes with coordination no. of 6, the
ligands occupy octahedral position to
minimize the repulsion from six electron pairs
around the central metal ion
Examples:
87
Shapes of tetra- and hexa-coordinated complexes
Coordination number of the
Shape of complex Example
central metal atom or ion
Tetrahedral
[Zn(NH3)4]2+
[CoCl4]2–
4
Square planar
[Cu(NH3)4]2+
[CuCl4]2–
88
Shapes of tetra- and hexa-coordinated complexes (cont’d)
Coordination number of the

Shape of complex Example
central metal atom or ion
Octahedral
[Cr(NH3)6]3+
6
[Fe(CN)6]3–
89
Isomer
Isomers are different compounds that have the same

molecular formula
• Isomers of complexes are classified into:
1. Structural isomers
2. Geometrical isomers
90
1. Structural isomers
Structural isomers are isomers that have different

ligands bonded to the central metal atom or ion
Example: Cr(H2O)6Cl3 has four structural isomers

which have different colours:
[Cr(H2O)6]Cl3 violet
[Cr(H2O)5Cl]Cl2 • H2O light green
[Cr(H2O)4Cl2]Cl • 2H2O dark green
[Cr(H2O)3Cl3] • 3H2O brown
91
2. Geometrical isomers
Geometrical isomers are isomers that have different
arrangement of ligands in space
• Only square planar and octahedral complexes have
geometrical isomers
(a) Square planar complexes
(i) Square planar complexes of the form [Ma2b2]
may exist in cis- or trans- form
92
Example:
Isomers in which two ligands of the same type occupy

adjacent corners of the square are called cis-isomer
Isomers in which two ligands of the same type occupy

opposite corners of the square are called trans-isomer
93
(ii) Square planar complexes of the form [Ma2bc] may

also exist in cis- or trans- form
94
(b) Octahedral complexes
(i) Octahedral complexes of the form [Ma4b2] may

exist in cis- or trans- form
95
96
Example:
97
(ii) Octahedral complexes of the form [Ma3b3] may

exist in fac- or mer- form
98
Example:
99
Shape of Chemical
Geometrical isomer
complex formula
[Ma2b2]
Square cis trans

planar
[Ma2bc]
cis trans
100
Shape of Chemical Geometrical isomer
complex formula
cis trans
[Ma4b2]
Octahedral fac mer
[Ma3b3]
101
Check Point 45-6

(a) Are there any geometrical isomers for a complex of the
form [Ma2b2]? Explain your answer with suitable
drawings.
(a) The square
(M represents the planar complex
central metalofion,
the form [Mab2bare
a and 2] may
two
differentexist
kindsin cis
of and trans forms.
ligands.)
Answer
There is no geometrical isomer for a tetrahedral

complex of the form [Ma2b2]
102

(b) The four isomers of chromium(III) (i.e. [Cr(H2O)6]Cl3,
(b)[Cr(H
Besides using colours, suggest two experimental methods to
2O)5Cl]Cl2 • H2O, [Cr(H2O)4Cl2]Cl • 2H2O and
distinguish
[Cr(H2O)between the four isomers of Cr(H2O)
3Cl3] • 3H2O) have different numbers of free Cl6–Cl 3: One
ions.
[Cr(H
way 2O)6]Cl3them
to distinguish , [Cr(H
is by2O) Cl]Cl
the5use 2 • H2O,silver nitrate(V) solution.
of acidified
When
[Cr(Hexcess
O) AgNO
Cl 3(aq)
]Cl • is added
2H O, to one mole
[Cr(H O) of3each
Cl ] • of the
3H O. isomers,
2 4 2 2 2 3 2
[Cr(H2O)6]Cl3 gives three moles of AgCl, [Cr(H2O)5Cl]Cl2 • H2O gives two
moles of AgCl, [Cr(H2O)4Cl2]Cl • 2H2O gives one mole of AgCl,Answer and
[Cr(H2O)3Cl3] • 3H2O does not give AgCl.
Another way to distinguish them is by measuring their electrical
conductivities. As the electrical conductivity depends on the number of
ions formed when dissolved in water, [Cr(H2O)6]Cl3 has the highest
electrical conductivity whereas [Cr(H2O)3Cl3] • 3H2O has the least.
103
Coloured Ions
• The natural colours of precious

gemstones are due to the existence
of small quantities of d-block
metal ions
• Most of the d-block metals form
coloured compounds and most of
their complexes are coloured too
∵the presence of incompletely filled
d orbitals in the d-block metal

104
ions New Way Chemistry for Hong Kong A-Level Book 4
104
• When a substance absorbs visible light of a certain

wavelength, light of wavelengths of other regions of the
visible light spectrum will be reflected or transmitted.
⇒ the substance will appear coloured
• The absorption of light energy is associated with electronic

transition (i.e. electron jumping from a lower energy level to
a higher one). The energy required for electronic transition
is quantized
105
• If the energy involved in electronic transition does not fall

into visible light region, the substance will not appear
coloured
• s-block and p-block elements are usually colourless

because an electronic transition is from one principle
energy level to a higher one
⇒ the energy involved is too high in energy and it falls

into ultraviolet region
106
• For the d-block elements, the five 3d orbitals are degenerate in
gaseous ions
• However, under the influence of a ligand, the 3d orbitals will split

into 2 groups of orbitals with slightly different energy levels
⇒ due to the interaction of the 3d orbitals with the
electron clouds of the ligands
107
• When a sufficient amount of energy is absorbed,

electrons will be promoted from 3d orbitals at lower
energy level to those at the higher energy level
• The energy required for the d-d transition falls within
the visible light spectrum.
⇒ This leads to light absorption, and reflects the

remainder of the visible light
⇒ d-block metal ions have specific colours
108
The colours of some hydrated d-block metal ions
Number of unpaired
Hydrated ion Colour
d electrons
0 Sc3+ Colourless
Ti4+
Zn2+
Cu+
1 Ti3+ Purple
V4+ Blue
Cu2+ Blue
2 V3+ Green
Ni2+ Green
3 V2+ Violet
Cr3+ Green
Co2+ Pink 109
The colours of some hydrated d-block metal ions
(cont’d)
Number of unpaired
Hydrated ion Colour
d electrons
4 Cr2+ Blue
Mn3+ Violet
Fe2+ Green
5 Mn2+ Very pale pink
Fe3+ Yellow
Co2+(aq) Zn2+(aq) Fe3+(aq) Mn2+(aq) Fe2+(aq) Cu2+(aq)
110
• For d-d electronic transition and absorption of visible light

to occur, there must be unpaired d electrons in the d-block
metal atoms or ions
⇒ Sc3+ and Zn2+ are colourless due to the empty 3d

sub-shell and the fully-filled 3d sub-shell
respectively
111
• The colours of hydrated metal ions are determined by the

oxidation states of the particular d-block elements
e.g. Fe2+(aq) is green while Fe3+(aq) is yellow
⇒ different oxidation states are caused by different

numbers of d electrons in the d-block metal ion
⇒ this has direct effects on the wavelength of the

radiation absorbed during electronic transition
112
Catalytic Properties of Transition Metals and their Compounds
The use of some d-block metals and their compounds as
catalysts in industry
d-block element Catalyst Reaction catalyzed
V2O5 or Contact process
V
vanadate(V)(VO3–) 2SO2(g) + O2(g) 2SO3(g)
Haber process
Fe Fe
N2(g) + 3H2(g) 2NH3(g)
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) +
113
113 New Way Chemistry for Hong6H 2O(l)
Kong A-Level Book 4
• d-block metals and their compounds exert their

catalytic actions in either heterogeneous catalysis or
homogeneous catalysis
• The function of a catalyst is to provide an alternative

pathway of lower activation energy
⇒ enabling the reaction to proceed faster than the
uncatalyzed one
114
Heterogeneous Catalysis
• In heterogeneous catalysis, the catalyst and reactants

are in different phases
• The most common heterogeneous catalysts are finely

divided solids for gaseous reactions
• A heterogenous catalyst provides a suitable

reaction surface for the reactants to come close
together and react
115
e.g.: Synthesis of gaseous ammonia from N2 and H2
N2(g) + 3H2(g) 2NH3(g)

• 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 is very small
⇒ the four reactant molecules have to collide in a
proper orientation in order to give products
⇒ the bond enthalpy of N ≡ N is very large
⇒ the reaction has a high activation energy
116
• In the presence of iron catalyst, the reaction

proceeds faster as it provides an alternative
reaction pathway
• The catalyst exists in a different phase from that of

both reactant and products
• The catalytic action occurs at the interface between

two phases, and the metal provides an active
reaction surface for the reaction to occur
117
The catalytic
mechanism of the
formation of NH3(g)
from N2(g) and H2(g)
118
Energy profiles of the reaction pathways in the

presence and absence of a heterogeneous catalyst
119
Summary:
• In heterogeneous catalysis, the d-block metals or

compounds provide a suitable reaction surface for the
reaction to take place
∵ the presence of partly-filled d-orbitals
⇒ this enables the metals to accept electrons from

reactant particles on one hand and donate electrons to
reactant particles on the other
120
Homogeneous Catalysis
• A homogenous catalyst is in the same phase as the

reactants and products
• The catalyst forms an intermediate with the reactants
⇒ it changes the reaction mechanism to a new one

with a lower activation energy
• The ability of d-block metals to exhibit variable

oxidation states enables the formation of the reaction
intermediates
121
• e.g. reaction between peroxodisulphate(VI) ions and

iodide ions
S2O82–(aq) + 2I–(aq) 2SO42–(aq) + I2(aq)
Ecell = +1.47 V
• The standard e.m.f. calculated for the reaction is a highly

positive value
⇒ there is high tendency for the forward reaction to occur
• However the reaction is very slow due to kinetic factors
122
• In catalytic process, Fe3+(aq) ions oxidizes I–(aq) to I2(aq)

with themselves being reduced to Fe2+(aq)
2I–(aq) + 2Fe3+(aq) I2(aq) + 2Fe2+(aq)
Ecell = +0.23 V
• The Fe2+(aq) are subsequently oxidized by S2O82–(aq) and

Fe3+(aq) ions are regenerated
2Fe2+(aq) + S2O82–(aq) 2Fe3+(aq) + 2SO42–(aq)

Ecell = +1.24 V
123
The overall reaction:
2I–(aq) + 2Fe3+(aq) I2(aq) + 2Fe2+(aq)
+) 2Fe2+(aq) + S2O82–(aq) 2Fe3+(aq) + 2SO42–(aq)
2I–(aq) + S2O82–(aq) I2(aq) + 2SO42–(aq)
• Fe(III) ions catalyze the reaction by acting as an

intermediate for the transfer of electrons between
peroxodisulphate(VI) and iodide ions
124
Energy profiles for the
oxidation of I–(aq) ions by
S2O82–(aq) ions in the
presence and absence of a
homogeneous catalyst
125
Check Point 45-7

Which of the following redox systems might catalyze the
oxidation of iodide ions by peroxodisulphate(VI) ions in an
aqueous solution?
Cr2O72–(aq) + 14H+(aq) + 6e– 2Cr3+(aq) + 7H2O(l)
E +2.01V
Systems with E greater than +0.54V and smaller than = +1.33V
are
MnOable
4
– to +
(aq) catalyze
8H + the oxidation
(aq) + 5e– of iodideMn
ions2+by peroxodisulphate(VI)
(aq) + 4H O(l) ions
in an aqueous solution. Hence, the following two redox 2systems are able to
catalyze the reactions. E = +1.52V
Cr2O+72–2e
Sn4+(aq) (aq)
– + 14H+(aq) + (aq)
Sn2+ 6e– 2Cr3+(aq) + 7H2O(l)
E = +0.15V
MnO4–(aq)
2– + 8H (aq)
– + 5e
2SO4 (aq)(aq) + 4H2O(l) E = +2.01V
Mn
+ – 2+
(Given: S2O8 (aq) + 2e 2–
I2(aq) + 2e– 2I–(aq) E = +0.54V)

Answer
126
The END
127

The First Transition Series

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The First Transition Series

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Chapter 45

The First Transition Series

The first transition series

• All contains incomplete d sub-shell (i.e. 1 – 9 electrons) in at

• Strictly speaking, scandium (Sc) and zinc (Zn) are not

• Cu shows some intermediate behaviour between transition

• Cu+ is not a transition

Relative energy levels of orbitals before

• Before filling electrons, the energy of 4s sub-shell is

⇒ 4s sub-shell is filled before 3d sub-shell

• Once the 4s sub-shell is filled, the energy will increase

⇒ The lowest energy sub-shell becomes 3d sub-shell, so

Electronic configurations of the first series of d-block elements

• Cr is expected to be [Ar] 3d44s2 but the actual

• This can be explained by the fact that a half-filled or

d-Block Elements as Metals

• d-block elements are typical metals

• Transition elements have similar atomic radii which

e.g. Mn is for conferring hardness and wearing resistance

Cr is for conferring inertness on stainless steel

Iron is used to make ships Tsing Ma Bridge is

The statue is made of alloy of copper and zinc

Titanium is used in making aircraft Jewellery made of gold

Atomic Radii and Ionic Radii

Variations in atomic and ionic radii of

• The atomic size reduces at the beginning of the series

• The atomic size decreases slowly in the middle of the series

• The atomic size increases at the end of the series

∵ the screening and repulsive effects of the 3d

• Remember that the electrons have to be removed from the

Comparison of Some Physical and Chemical

Densities (in g cm-3) of the s-block metals

• d-block metals are generally denser than the s-block

• The densities increase generally across the first series of

• 1st I.E. of d-block metals are greater than those of s-block

∵ the d-block metals are smaller in size than the s-block

∵ the electrons are come form the inner fully-filled electron

• The first few successive I.E. for d-block elements do not

∵ Going across the first transition series, the nuclear charge

⇒ The additional screening effect of the additional 3d

• Successive ionization enthalpies exhibit a similar

• The increases in the 3rd and 4th ionization enthalpies

Check Point 45-1

Check Point 45-1 (cont’d)

(b) The third ionization enthalpy of Mn is higher than that

Electronegativity values of the s-block metals

• The electronegativity of d-block metals are generally

∵ Generally, d-block metals have smaller atomic radii

• The electronegativity shows a slight increase generally

∵ Gradual increase in effective nuclear charge and

⇒ The closer the electron shell to the nucleus, the more

Melting Point and Hardness

Melting points (°C) of the s-block metals and

• The melting points of the d-block metals are much higher

1. d-block metal atoms are small in size and closely packed in

2. Both 3d and 4s electrons of d-block metals participate in

• The hardness of a metal depends on the strength of the

∵ The metallic bond of d-block metals is stronger

⇒ d-block metals are much harder than the s-block

Check Point 45-2

Reaction with Water

• Generally, s-block metals (e.g. K, Na & Ca) react with

• d-block metals react only very slowly with cold water.