12.

1 CHARACTERISTIC PROPERTIES OF TRANSITION ELEMENTS

Objectives
By the end of the subtopic learners should be able to:
 Explain what is meant by transition, in terms of d-block element forming one or
more stable ions with incomplete d-orbitals.
 Analyse the electronic configuration of the first row transition elements and
their ions.
 Recognise that the atomic radii, ionic radii and first ionisation energies of the
transition metals are relatively invariant.
 Contrast qualitatively the melting point, density, atomic radius, first ionisation
energy and conductivity of the transition elements with those of calcium as a
typical s-block element.
 Describe the tendency of transition elements to have variable oxidation states.

Introduction to transition elements

• Transition metals are elements found in the d-block of the periodic table but are
more precisely defined as elements that can form stable ions which have
incomplete 3d orbitals.
• This definition excludes Zinc and Scandium to be part of transition elements
because:
1. Zinc ion has a full d-orbital,
Zn+2 = 1s2, 2s2, 2p6, 3s2, 3p6, 3d10, 4s0

2. Scandium ion has an empty d-orbital,

Sc+3 = 1s2, 2s2, 2p6, 3s2, 3p6, 3d0, 4s0

Characteristic properties of transition elements

 Transition elements has the following properties:
o Have variable oxidation states
o Form coloured compounds
o Are metals with high boiling and melting points
o Can bond using two different orbitals (4s and 3d)
o Have high densities compared to non-transition metals
o Are good catalysts.
Fig 12.1.1: Location of Transition elements on the Periodic Table

1. Electronic configuration
 There are two electronic configuration in transition chemistry and these are:
o Electronic configuration of elements
o Electronic configuration of ions

a. Electronic configuration of elements

 The outer electronic configuration of elements in the first row of the d-block is as
follows:

Fig 12.1.2: Electronic configuration of transition element

 Note the unusual structures of chromium and copper. The 4s and 3d subshells are
very similar in energy and therefore it is easy to promote electrons from the 4s into
the 3d orbitals.
  In chromium the 4s13d5 structure is adopted because the repulsion between two
paired electrons in the 4s orbital is more than the energy difference between the
4s and 3d subshells. It is thus more stable to have unpaired electrons in the higher
energy 3d orbital than paired electrons in the lower energy 4s orbital.

 In copper and zinc the 3d subshell is actually lower in energy than the 4s subshell.
The 3d orbitals are thus filled before the 4s orbital. Thus copper adopts a 4s 13d10
configuration.

b. Electronic configuration of ions

 In all ions of d-block elements, the 3d subshell is lower in energy than the 4s
subshell so the 4s electrons are always removed first. 3d electrons are only
removed after all 4s electrons have been removed.

 Some examples of electronic configurations of transition metal ions are shown

below:

Fig 12.1.3: Electronic configuration of transition ions

2. Atomic Radii
 Transition elements show slight changes in there atomic radii from left to right
across a period.
 Since the nuclear charge of the elements increases across a period, the atomic radii
is expected to decrease.
 But as the electrons are added to an inner 3d-orbital which is between nucleus and
the 4s-orbital, the size of the size of the atom changes slightly.
Fig 12.1.4: Atomic radius of transition metals

3. Ionic Radii
 To compare the ionic radii of transition elements, a common oxidation state
should be used.
 For this purpose the +2 oxidation state is used.
 Generally the ionic radii of transition metals gradually decrease as the nuclear
charge increases across the period.
 The general trend is shown by the grey dotted line while the purple line show the
actual change in the radii.

Fig 12.1.5: Ionic radius of transition metals

4. Ionisation Energy
 From left-to-right period 4 (transition metals), proton number increases which
results in a slight increase in the effective nuclear charge which results in the
slight increase in the ionisation energy.
 For third ionisation energy, the more rapid the 3d electrons are removed, the
more significant the effective nuclear charge becomes and therefore shows are
greater magnitude from element to element.

Fig 12.1.6: First three ionisation energies of transition elements

5. Comparison with an s-block element

Table 12.1.1: Comparison of transition elements with calcium

Property Transition element Calcium
Melting point Very high (over 1000⁰C ) Lower (850⁰C for Ca)
Density Very High Low
Atomic radius Smaller Larger
2+ Smaller Larger
Ionic radius (M ion)
First ionisation energy Larger Smaller
Electrical conductivity Good, but poor than Ca Very good
6. Variable Oxidation States
 The oxidation state formed by an element in its compounds is determined by the
maximum number of electrons the element lose without requiring so much energy.

 S-block elements only form one stable oxidation state in their compounds. They
lose all their valence electrons easily but cannot lose any more electrons since
there is a large amount of energy required to remove the electrons from the inner
shell.

Table 12.2.2: Examples of oxidation states of s-block elements

Element Oxidation state
Na +1
Mg +2

 In the d-block elements, however, there are often a large number of valence
electrons and removing them all would require so much energy that it would be
unfeasible. It is usually only possible to remove some of the valence electrons.
 All d-block elements can give up their 4s electrons fairly easily that is why the
oxidation state +2 is common to all transition elements.
 The maximum oxidation state of an element correspond to the number of
electrons available for bonding. Chromium has a maximum oxidation state of VI
and is due to the fact that 6 electrons are available for bonding (3d54s1).
 There is an increase in the maximum oxidation states from Sc to Mn because of
the increase of electrons which can be used in chemical bonding.
 From Mn to Zn the maximum oxidation states decreases due to the fact that
paired electrons will no longer be available for bonding and therefore as we
move to the right the number of paired electrons increases thus cause a
decrease in the number of electrons available for chemical bonds.

The oxidation states most commonly formed by the first-row d-block elements are as
follows:

Table 12.1.3: Oxidation states of transition elements

Sc Ti V Cr Mn Fe Co Ni Cu Zn
+1 +1 +1 +1 +1 +1 +1 +1
+2 +2 +2 +2 +2 +2 +2 +2 +2
+3 +3 +3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4 +4 +4 +4
+5 +5 +5 +5 +5
+6 +6 +6
+7
The ones in blue are the common oxidation states
 Note that scandium only forms +3 ions (d0). This is because the low effective
nuclear charge on scandium enables all three valence electrons to be removed
fairly easily.
 Note also that zinc only forms +2 ions (d10). This is because the high effective
nuclear charge on zinc prevents any 3d electrons from being removed.
 All the other elements form at least one stable ion with partially filled d-orbitals,
and it is this property which defines a transition metal.