13.

1) PHYSICAL PROPERTIES OF
FIRST ROW TRANSITION ELEMENT
A TRANSITION ELEMENT IS STRICTLY DEFINED AS AN
ELEMENT THT FORMS AT LEAST A STABLE SIMPLE ION
WITH INCOMPLETE OR PARTIALLY FILLED d ORBITALS
PARTIALLY MEANS NEITHER EMPTY NOR FULL

TRANSITION ELEMENT AND THEIR

IONS
d- block
element
Transition metal

Ti
Sc

V
Cr

Mn Fe

Co

Ni

Cu

Zn

Scandium and zinc are not transition elements based on the chemical
definition given.
Each of these metals forms just one ion.
Sc : [Ar] 3d 4s
3d subshell)

Sc : [Ar}

(empty

Atomic size
The decrease in atomic size does not apply to the
d-block elements
Atomic size of the 1st row d-block elements are
shown in table 1. With the exception of scandium
and titanium, the atomic radius of the d-block
elements are approximately the same across the
period.
In the series of 1st row d-block elements, additional
electrons go into an inner electron shell (3d
subshell). At the same time, the number of the
electrons in the outermost shell) (4s orital) remain
constant.

Table 1
Element
(symbol)

Proton
number

Electronic
configuration

Atomic radius
(nm)

Scandium (Sc)

21

[Ar] 3d 4s

0.160

Titanium (Ti)

22

[Ar] 3d 4s

0.146

Vanadium (V)

23

[Ar] 3d 4s

0.131

Chromium ( Cr)

24

[Ar] 3d 4s

0.125

Manganese
(Mn)

25

[Ar] 3d 4s

0.129

Iron (Fe)

26

[Ar] 3d 4s

0.126

Cobalt (Co)

27

[Ar] 3d 4s

0.125

Nickel (Ni)

28

[Ar] 3d 4s

0.124

Copper (Cu)

29

[Ar] 3d 4s

0.128

Zinc ( Zn)

30

[Ar] 3d 4s

0.133

These inner 3d electrons shield the outer 4s electrons from the nuclear charge much more effectively than
outer shell electrons can shield one another thus,the effect of increased nuclear charge is roughly cancelled
by screening effect of the electrons in the 3d orbitals. This means tht the effective nuclear remains almost
constant. Thus, the atomic (metallic) radii do not change very much for the first row d-block elements.
(figure 1)

atomic radius
180
160
140
120
100
80
60
40
20
0
Sc Ti V Cr Mn Fe Co Ni Cu Zn

atomic radius

Melting and boiling point

At the 1st row d-block elements except (zinc) have high melting points and
boling points (figure 2) because of strong metallic bonds in the metal
lattice.

4000
3500
3000
2500
2000
1500
1000
500

0
Sc Ti V Cr Mn Fe Co Ni Cu Zn

boiling point
melting point

Small energy difference between the electrons in the 3d

and 4s subshells enables these electrons to contribute to
the sea of delocalised electrons and hence results in strong
metallic bonding. In contrast,potassium from the same
period is soft and has a low melting point of 64C and
boiling point of 774C as only one 4s electron is involved in
the metallic bond formation. similarly, calcium has relatively
low melting point(840C) and boiling point (1484C).
Melting point and boiling point of manganese and zinc are
lower-extra stability of the half-filled and completely filled d
subshell. These d electrons are less available, leaving only
the 4s electron to contribute to the sea of delocalised
electrons in metallic bonding.

Densities
The densities of the first series dblock elements increase from
scandium to copper and then dips for
zinc.
eleme
nt

Sc

density

3.00

Ti
4.51

Cr

Mn

Fe

Co

Ni

Cu

Zn

6.10

7.19

7.43

7.86

8.90

8.90

8.96

7.14

This means the densities of d-block elements are high compared with
other metals
( for example, group 1 and 2 elements). The high
densities of these elements relatively small atomic radii of their
atoms. as a results, the atoms are tightly packed together in the
crystal lattice.
When across the 1st row d-block elements, the density increases
gradually as shown in figure 3.

density
10
9
8
7
6

density

5
4
3
2
1
0
Sc

Ti

Cr

Mn

Fe

Co

Ni

Cu

Zn

In passing from scandium ( metallic

radius=0.160 nm) to copper (metallic
radius= 0.128 nm), there is a slight
decrease in atomic radius. As
density=mass over volume, the slight
decrease in atomic radius together
with an increase in relative atomic
mas causes the increase in density.

Successive Ionisation
Energies
The 1st and 2nd ionisation energies of
the first series d-block elements
increase slightly across the series as
the poton numbers increases.(figure
4)

8000
7000
6000
5000

1st ionisation energy

2nd ioniation energy
3rd ionisation energy
4th ionisation energy

4000
3000
2000
1000
0
Sc Ti

Cr Mn Fe Co Ni Cu Zn

 In forming M(g) ions (1st ionisation energy) and

M(g)ions (2nd ionisation energy)of the d-block
elements,the 4s electrons are the first to be
removed.the slight increase in the 1 st and 2nd
ionisation energies on going across d-block series
bcause the 4s electrons are shielded frm the
increasing nuclear charge by the increasing
screening effect of the inner 3d electrons.
The 2nd ionisation energies for chromium and copper
is higher than expected-bcause the 2 nd electron is
removed from 3dnand 3d orbitals respectively.
Half-filled d orbital (d)and fully filled d orbital (d)
have extra stability. A higher energy is required to
remove electrons from these orbitals.

3s

3p

3d

4s
Cr

2nd electron
removed from the 3d orbitals

3s

3p

3d

4s
Cu

2nd electron
removed from the 3rd orbitals

 The 3rd and 4th ionisation energies from

scandium to zinc show a larger increase.
- Because the electrons in 3d orbitals are
now being removed.
- The remaining electrons gives a relatively
smaller shielding effect.
- The effective nuclear charge (increasing
nuclear charge and decreasing shielding
effect) increases more significantly frm
one element to the next across the dblock elements.

 The 3rd ionisation energy of

manganese (3260kJ mol) is higher
than tht of chromium (2990 kJmol)
and iron (2960 kJmol) because the
3rd electron is removed from the
stable Mn ion which has the
electronic configuration [Ar] 3d.
Similarly for Zn, more energy is
required to remove an electron from
the stable Znion with the electronic
configuration [Ar] 3d.

 The 4th ionisation energy of scandium is

very high- bcause 4th electron must be
removed frm the inner sub-shell of a stable
noble gas configuration.
The 4th ionisation energy of titanium (4170
kjmol) is very much lower than of the
scandium(7110 kjmol)-bcause the 4 th
electron is removed from the d-orbitals and
not from the full p orbitals of a noble gases.

 The successice ionisation energies for a

given metal in the d-block series increases
gradually- bcause the electrons in the 4s
and 3d sub-shells differ only slightly in
terms of energy level.
For example:750(1st),1960,3560,5690(4th
ionisation energy)
Bcause of this, an atom of d-block element
can lose electrons from both the outer 4s
and inner 3d sub-shells to form ions

CHEMICAL
PROPERTIES OF
TRANSITION
ELEMENTS.

1) Exhibit variable oxidation state.

- due to the small difference of energy (small gap)
between the 4s and 3d subshell, electrons are able to
transfer from 4s to 3d easily. Therefore, transition
elements have variable oxidation state.
Ti
+2
+3
+4

+2
+3
+4
+5

CR

+2
+3
+4
+5
+6

Mn

+2
+3
+4
+5
+6
+7

Fe

+2
+3
+4
+5
+6

Co

Ni

Cu

+2
+3
+4
+5

+2
+3
+4

+1
+2

Oxides of transition elements.

- Insoluble in water.
- Covalent character.

Ti

Cr

M
n

Fe

C
o

Ni

C
u

FeO

CoO

NiO

CuO

NiO2

Cu2O

MnO
Ti2O3

V2O3

Cr2O3
MnO2
Mn2O

TiO2

V2O5

CrO3

Mn2O
7

Fe2O3

Co2O
3

2) Forms complexes.

Forms oxoanions.
Oxoanions- formed due to high charge densities
of ionisation.

Simple ions: low oxidation states; ex: +1,+2,+3

Usually form basic electrovalent oxides.

Whereas, oxidation states of +4 to +7 do not form

simple ions.
Usually form acidic covalent oxides, except for +4,
it is amphoteric.

Oxoanions. (complex ions)

Ti

V
VO2+

TiO2+

Cr

M
n

CrO42-

MnO4-

VO2+
VO3+

Fe
FeO42-

Cr2O72

MnO4

2-

+2 and +3 Oxidation states.

The relative stability of the

oxidation state
Most oxidation states of the transition elements are
+2 & +3
Ti , V , Cr & Fe +3 oxidation state is more stable than
+2 oxidation state
Mn , Co , Ni & Cu +2 oxidation state is more stable
than +3
Because , as go across the d block , it gets more
difficult to remove a third e Due decrease in size of the atom & increase in
nuclear charge
Oxidation state +4 and above are relatively less
stable because energies involve too high

Standard Reduction Potentials & the

Relative Stability of Aqueous Ions
Most oxidation states of transition element are
+2 & +3.
Relative stability of +2 & +3 states can predict
by looking at the standard electrode potential.
Refer to graph page 223 no.3
Half- cells where the E values are less than
+1.23V, oxygen from air will oxidize the +2 state
to +3 state ( pg. 223 no 4 e.g..)
Half-cells where the E is more positive than
+1.23V , the +3 than +2 state( pg. 223 no 5
e.g..)

Redox properties of the

various oxidation state
Lower oxidation states of transition
elements are reducing as shown by
their negative standard electrode
potentials.
The more positive the E value , the
stronger the oxidizing agent.
Refer to (pg. 224 no 2-4)

3) Form coloured ions.

Why are ions of transition elements coloured?

- Their d-subshell is partially filled with electrons.

2 2
x y

d d
xy

xz

d d
yz

2 2
x y

xy

xz

yz

WHEEL OF COMPLEMENTARY
COLOURS.

4) Act as a catalyst.

Catalyst can be divided into two types:

- Homogeneous
those in the same physical phase as the other reactants
e.g: all in solution together in the same solvent, or all are
gases.
Most transition elements are effective homogenous catalys.
Because: 1)oxidation able to interconvert readily.
2) 4s and 3d orbitals are close in terms of energy
Therefore, transition elements are useful as redox catalysts.

Heterogenous
those in a different physical phase to the rest of the
reactants.
e.g: two different liquids in contact with catalysis occurring
at the interface between them, or more commonly a solid
catalyst and a solution, or a solid and gases
Occurs on the surface of the solid.
Transition elements are effective heterogenous because:
1) have many empty 3d and 4s orbitals; can form temporary
bonds with the reactant molecules.
Mechanism:
- adsorption of reactants onto the surface of catalyst
- breaking and formation of bonds
- desorption of products from the surface of the catalyst

5) Paramagnetic.

- Because transition elements have unpaired electrons.

- Weakly attracted by external magnetic field.
- Strength of paramagnet is affected by the number of unpaired
electrons.
Strength of paramagnet increase as the number of unpaired
electrons increase.
p/s: paramagnets always point permanently to the poles of the Earth
(compass)

Formation of Complex Ions and Ligand

Exchange
A complex ion = an ion of a central metal
cation bonded to a group of atoms/
molecules / ions (ligand) by coordinate
bonds
Eg. of complex ion (Cu(NH3)4)2+
Formation of complex, the ammonia
molecule donate their lone pair electrons
to empty orbitals in Cu2+ ion to form
coordinate bonds
The metal cation acts as Lewis acid &
ammonia molecule acts as Lewis base

13.3 NOMENCLATURE
AND BONDING OF
COMPLEXES.

NAMING OF
COMPLEXES
A ligand or complexing agent , is a polar molecule or ion bonded to a central
metal ion.
A complex ion is a polyatomic species consisting of a central metal ion
surrounded by several ligands.
Naming complex ion:
a) anionic ligands have names ending in o.
i) ide
o. E.g: chloride= chloro
b)Neutral ligands are named as the molecule with these notable exceptions:
i)HO= aquo
ii)NH= ammine
c)the number of ligands in a complex are specified using prefixes:
i)di = 2
ii)tri = 3
iii) tetra = 4
iv)penta = 5
v) hexa = 6

 The ligands are named first (prefix), in alphabetical order followed by

the name of the metal ion, all in one word with no space between
them.
Oxidation number of metal cation is written in Roman numerals with
a bracket after the metal cations name.
prefix + metal ion name + oxidation number
The name of an anionic complex ion ends in ate,
ex: Titanium = titanate

The prefix bis,tris and tetrakis are used to replace di, tri and tetra if a
ligand itself already has the later prefix.
Ex: [ Ni(C)] =TRIS-ETHANEDIOATENICKELATE (II)

 Example: Name the following complex ion:

[Fe(CN)]^31.The overall charge on the ion is negative, so the
metal name becomes ferrate.
2.The oxidation number needs to be worked out
considering that the cyanide ion has the formula CN-.
There are six cyanide ions = 6-. The overall charge on
the complex ion is 3- therefore the metal ion has a
charge of [3- = x+ (6(-1))],i.e. oxidation state (III)
There are six cyanide ions, therefore hexacyanoThe complex ion's name is hexacyanoferrate (III)

BONDING OF COMPLEXES

In formation of complexes,
central metalis cation uses its empty orbitals in valence shell to accept lone pair
electron
from the ligand to form coordination.
Ex: hexacyanoferrate (II) complex ion [Fe(CN)6]^4-.
Electronic configuration of Fe^2+ = [Ar]3d6.

3d

4s

1st step : pairing of electrons

2nd step: empty orbitals used to accept lone pairs.

4p

CLASSIFICATION OF
Ligand have lone pair electrons that can be donated to a
LIGANDS
metal cation to form coordinate bonds.
Classified according to no of lone pair that can be
donated to central metal cation.
3 types:
i)monodentate ligand
ii)bidentate ligand
iii)hexadentate ligand

MONODENTRATE LIGAND
i. Has one donor atom
ii. forms one coordinate bond per unit ligand.
iii. The term "monodentate" can be translated as "one tooth," referring to the
ligand binding to the center through only one atom.
iv. Ex: HO , water (referred to as aqua when it is a ligand)

BIDENTATE LIGAND
i.
ii.
iii.

Have 2 donor atoms

Form 2 coordinate bond oer unit ligand
Ex: Ethane-1,2-diamine

HN CH CH NH
Nitrogen atoms on the edges have two free electrons that can be
used to bond to a central metal ion

iv)
Bidentate ligand can form ring like structure. These ligand known as chelating
agents and the complexes
are called chelate compounds/chelates.

HEXADENTATE LIGAND
iv. EDTA or ethylenediaminetetraacetate is a hexadentate ligand whc is used in its
anionic form EDTA^4-.
v. Have 6 donor atom.

GEOMETRY COMPLEXES

General geometry depend on no of coordinate bond surrounding central metal cation.

Coordination number: no of coordinate bond surrounding cental atom.

Coordination number of 2

Linear
Ex: [CuCl] : Cl

Coordination

Cu

Cl

number of 4

Tetrahedral
Different geometries are dur to different type of hybridisation.
Tetrahedral: sp^3 hybrisation
Square plannar : dsp^2 hybridistion

Square
plannar

tetrahedral

COORDINATION OF NUMBER 6

octahedral

octahedra
l

Uses of chromium

increase tensile strength of steel and increase steels resistant to corrosion by forming oxide
layer.
Alloy of chromium with vanadium and tungsten is used in high speed cutting tools.
Make electrical heating elements
Several chromium compounds are used as catalysts for processing hydrocarbons. For
example the Phillips catalyst, prepared from chromium oxides, is used for the production of
about half the world's polyethylene

Uses of titanium

Lighter than steel and more resistant to corrosion

Titanium(IV) oxide white solid used as white pigmnt in paints.

Uses of Manganese and Cobalt

main use in manufacture if alloys

Used to make speed cutting tools.
Alloy of cobalt and samarium (Sm) is used to make permanent magnets.

USES OF FIRST ROW TRANSITION

ELEMENTS
1) Widely used in alloys.
2) Used in making aircrafts, space capsules and nuclear
reactor.
3) Used in hip and knee replacement units and also bone
implants
4) Chromium used in electroplating and also high speed
cutting tools
5) Nichrome used as electrical heating element.
6) Used to make stainless steels (alloy)
7) Cobalt-60 (isotope) used as radiation for cancer
treatments.
8) Nickel used as catalyst in the production of margarine.
9) Cupro-Nickel used for making coins.
10) Alnico used to make strong permanent magnets.
11) Copper used in electrical wiring
12) Copper used in domestic hot water pipes.