D.

APPLIED CHEMISTRY
• The topics to be covered are:
12. Transition elements
13. Phase equilibria
14. Environmental chemistry
15. Nano technology
 12.0 TRANSITION
ELEMENTS
12.1 Characteristic properties of transition elements
 OBJECTIVES

By the end of the subtopic, you 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
d orbital.
• This definition excludes Zinc and Scandium (from 3d row) to be part of transition
elements because:
• Zinc ion has a full d-orbital,
Zn+2 = 1s2, 2s2, 2p6, 3s2, 3p6, 3d10, 4s0

• 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:
• Have variable oxidation states
• Form coloured compounds
• Are metals with high boiling and melting points
• Can bond using two different orbitals (4s and 3d)
• Have high densities compared to non-transition metals
• Are good catalysts.
Fig 12.1.1: Location of transition elements on the periodic table
Electronic configuration
• There are two electronic configuration in transition chemistry and these are:
• Electronic configuration of elements
• Electronic configuration of ions

Electronic configuration of elements

• The outer electronic configuration of elements in the first row of the d-block is as follows:
• 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 4s13d10 configuration.
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

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
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
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
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
Ionic radius (M2+ ion) Smaller Larger

First ionisation energy Larger Smaller

Electrical conductivity Good, but poor than Ca Very good

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 red 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.
 ASSESSMENT EXERCISE 12.1 CHARACTERISTIC
PROPERTIES OF TRANSITION ELEMENTS
1. Explain why Sc and Zn are not classified as transition metals. [2]
2. Give the full electronic configuration of a
a. Copper atom
b. Iron(III) ion
c. Manganese atom
d. Zinc (II) ion
e. Cobalt atom
f. Chromium atom [6]

3. What feature of transition metals allows them to show variable oxidation states? [2]
4. When FeCl3 and K 4 Fe(CN)6 are mixed together, a coloured compound that can be used as a
dye is obtained. Give the oxidation states of iron in the two compounds and the name of the
compound.
a. FeCl3
b. K 4 [Fe(CN)6 ] [2]