FIRST ROW

TRANSITION ELEMENTS
What is a Transition Element?
• A transition element (or metal) is one which forms one or more stable
ions which have incompletely filled d orbitals.
THE FIRST ROW TRANSITION ELEMENTS
The First Row Transition Elements
ELECTRON The electron
SYMBOL NAME configuration of Cr and
CONFIGURATION
Cu do not follow the
Sc Scandium [Ar] 3d14s2 expected pattern of filling
Ti Titanium [Ar] 3d24s2 the d sub-shell.
V Vanadium [Ar] 3d34s2
Cr Chromium [Ar] 3d54s1
Mn Manganese [Ar] 3d54s2
Fe Iron [Ar] 3d64s2
Co Cobalt [Ar] 3d74s2
Ni Nickel [Ar] 3d84s2
Cu Copper [Ar] 3d104s1
Zn Zinc [Ar] 3d104s2
Are all members of this Row Transition
Elements by Definition?
• Scandium and zinc don't count as transition metals - even though they are
members of the d block.
• Scandium has the electronic structure [Ar] 3d14s2. When it forms ions, it always
loses the 3 outer electrons and ends up with an argon structure. The Sc3+ ion has no
d electrons and so doesn't meet the definition.
• Zinc has the electronic structure [Ar] 3d104s2. When it forms ions, it always loses the
two 4s electrons to give a 2+ ion with the electronic structure [Ar] 3d10. The zinc ion
has full d levels and doesn't meet the definition either.
• By contrast, copper, [Ar] 3d104s1, forms two ions. In the Cu+ ion the electronic
structure is [Ar] 3d10. However, the more common Cu2+ ion has the structure [Ar]
3d9.
• Copper is definitely a transition metal because the Cu2+ ion has an incomplete d
level.
Transition Metal Ions
• When d-block elements form ions, the 4s electrons are lost first.
Electronic structure for Co2+:
The 2+ ion is formed by the loss of the two 4s electrons.

Co [Ar] 3d74s2

Co2+ [Ar] 3d7

Electronic structure for V3+:

The 4s electrons are lost first followed by one of the 3d
electrons.

V [Ar] 3d34s2

V3+ [Ar] 3d2

Variable Oxidation States in the Transition
Elements
• Iron has two common oxidation states (+2 and +3) in, for example,
Fe2+ and Fe3+. It also has a less common +6 oxidation state in the
ferrate(VI) ion, FeO42-. Fe [Ar] 3d64s2
Fe2+ [Ar] 3d6
Fe3+ [Ar] 3d5
• Manganese has a very wide range of oxidation states in its
compounds. For example:
+2 Mn2+

+3 Mn2O3

+4 MnO2

+6 MnO42-

+7 MnO4-
Varying Oxidation states
 Vanadium
Vanadium has oxidation states in its compounds of +5, +4, +3 and +2. The source of vanadium in the +5 oxidation
state is NH4VO3. The exact vanadium ion present in the solution is very complicated, and varies with the pH of the
solution. The reaction is done under acidic conditions when the main ion present is VO2+ - called the
dioxovanadium(V) ion.
If you do the reaction in a small flask, it is normally stoppered with some cotton wool. This allows hydrogen (produced
from a side reaction between the zinc and acid) to escape. At the same time it stops much air from entering. This
prevents re-oxidation of the lower oxidation states of vanadium (particularly the +2 state) by oxygen in the air.
The reaction is usually warmed so that the changes happen in a reasonable time.

The reduction is shown in two stages. Some individual important colours are shown, but the process is one
continuous change from start to finish.
The reduction from +5 to +4

It is important to notice that the green colour

you see isn't actually another oxidation state. it is
just a mixture of the original yellow of the +5
state and the blue of the +4.
The reduction from +4 to +2
The colour changes just continue

The reason for the inverted commas around the vanadium(III) ion is that this is almost certainly a
simplification. The exact nature of the complex ion will depend on which acid you use in the reduction
process. If you use hydrochloric acid, you get a ligand exchange reaction to give [V(H2O)4Cl2]+. This causes
the green colour in the vanadium(III) solution.

The vanadium(II) ion is very easily oxidised. If you remove the cotton wool from the flask and pour some
solution into a test tube, it turns green because of its contact with oxygen in the air. It is oxidised back to
vanadium(III).
If it is allowed to stand for a long time, the solution eventually turns blue as the air oxidises it back to the
vanadium(IV) state - VO2+ ions.
Adding nitric acid (a reasonably powerful oxidising agent) to the original vanadium(II) solution also
produces blue VO2+ ions. The vanadium(II) is again oxidised back to vanadium(IV).
Characteristics of Transition Elements
Some have typical metallic properties, some have unique properties
• Form compounds with different oxidation states
• Their ions form coloured compounds
Most compounds and ions of
• Their ions form complex ions transition elements are
paramagnetic: when placed in a
• They are good catalysts magnetic field, they align
themselves with the field. They
• High density do not retain the magnetism.
• Very high melting and boiling points Fe, Co and Ni are ferromagnetic.
They retain permanent
• Have magnetic properties magnetism after the magnetic
field has been withdrawn
Why Fe, Co and Ni are ferromagnetic
• the magnetic properties of elements arises due to the presence of
unpaired electrons in its outer most valence shell.

• In case of Fe, Co and Ni , the magnetic moment due to unpaired

electron spins are aligned parallel to

• The external magnetic field more efficiently results in an exceptionally

strong reinforcement of paramagnetism.

• These substances are therefore, much more paramagnetic than the

rest of the elements ,are said to be ferromagnetic.
Physical Properties
Element Ti V Cr Mn Fe Co Ni Cu
1st Ionisation energy/ kJmol-1 661 648 653 716 762 757 736 745
Atomic Radius/nm 0.132 0.122 0.117 0.117 .0116 .0116 0.115 0.117
Ionic Radius of 2+ ions/nm 0.090 0.090 0.085 0.080 0.076 0.078 0.078 0.069

First ionisation energy generally increases by a small amount. Atoms of each successive element have one
more proton in their nucleus
Transitions Elements and Calcium
• Ca is in the s block, it’s a group II element and it is placed just before
the d block elements. They are markedly close yet have differences
between them
Ca Fe Ni
Melting point/oC 839 1540 1450
Density / gcm-3 1.55 7.86 8.90
Atomic radius/nm 0.197 0.116 0.115
Ionic radius/nm 0.099 0.076 0.078
First Ionisation 590 762 736
Energy/kJ mol-1
• The transition elements are harder and have higher melting points than Ca. This reflects
the stronger metallic bonding in transition elements compared with Ca. Ca can only
release two outer s electrons to the sea of delocalised electrons but transition elements
can release from both the s and d sub-levels. There is greater force of attraction also due
to the decrease in size.

• The atomic and ionic radii of Ca are much higher than the transition elements. This is
because of the filling of the d sub-level in transition elements. These electrons in the d
sub-level are less effective at shielding the outer electrons from the nuclear charge. There
is a greater force of attraction between the nucleus and the outer electrons which tends
to pull the electrons closer to the nucleus.

• The first ionisation energies of transition elements are higher than that of Ca because of
this relatively greater force of attraction between the nucleus and the outer electrons.

• The transition elements are denser than Ca, this is due to the transition element ions
having smaller radii than Ca.

• Electronegativity in the transition elements is higher successively across the period as the
elements become less metallic. They are more electronegative than Ca.
Electrical Conductivity of transition elements
• Most are good conductors of electricity. Those with a single outer s
electron and a half-filled or completely filled d shell are especially
good.
• Therefore Cu and Cr are the better conductors.
Is Ca suitable for electrical wiring?
Summary
• Transition elements form one or more ions with an incomplete d sub-shell
of electrons
• When transition element forms an ion, the electrons are first lost from the
4s sub-shell and then from the 3d sub-shell.
• Transition elements exist in various oxidation states, form coloured
compounds(containing complex ions), and often have characteristic
magnetic properties and catalytic activity
• Across the first row of transition elements, the changes in atomic and ionic
radius and first ionisation energy are relatively small. This is because each
electron added goes into a d sub-shell and so the shielding effect is
minimised.
• The physical properties of transition elements differ from those of a typical
s block element because of the presence of the d sub-shell.