TRANSITION METALS

A transition metal is a d block element which forms one or more stable ions with an incomplete d
electron sub shell.

Sc [Ar] 3d14s2

Ti [Ar] 3d24s2

V [Ar] 3d34s2

Cr [Ar] 3d54s1

Mn [Ar] 3d54s2

Fe [Ar] 3d64s2

Co [Ar] 3d74s2

Ni [Ar] 3d84s2

Cu [Ar] 3d104s1

Zn [Ar] 3d104s2

Sc and Zn are not transition elements because Sc forms only one ion with no electrons in the d sub shell
and Zn forms one ion and has a complete 3d sub shell.

NB: configurations for Cu and Cr are an exception because this arrangement is more stable for
them.

NB: when transition metals lose electrons the 4s electrons are lost first.
The range of oxidation states

Transition elements may have several different oxidation states. The most common ox state is
+2. Mn has the most number of ox states.

Higher oxidation states are found in complex ions.

Ti 1 2 3 4

V12345

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

Cu 1 2 3

Characteristics of transition metals

Transition metals have typical metallic properties but have some properties which set them apart
from other metals:

1. They form compounds with different ox states

2. Their ions form coloured compounds
3. Their ions form complex ions
4. They are often good catalysts
5. They have high density
6. They have high melting and boiling points
7. They have magnetic properties- most compounds and ions are paramagnetic (align
themselves in a magnetic field but do not retain their magnetism when the field is
removed). Fe, Co and Ni are ferromagnetic (they retain permanent magnetism even
when the field has been withdrawn).
First ionisation energy, density, melting point, electronegativity, atomic and ionic
radii of transition metals compared to Ca.

The transition elements are harder and have higher melting points than calcium. Calcium
can only release two outer electrons to form the delocalized “sea of electrons” but
transition elements can release electrons from both the 4s and 3d subshells, therefore
would have a greater attraction.

The transition metals show SMALL changes in ionization energy, atomic and ionic radii
from Ti to Cu.

Ionization energy generally increases but not by much. The nuclear charge or attraction
should increase with each added proton however the d electron shielding makes the
nuclear attraction less effective and it becomes easier to remove and electron.

The atomic and ionic radii of calcium are much larger than the corresponding radii for
typical transition elements. Across the transition elements, the nuclear attraction is
greater therefore the size would be smaller than Ca. However shielding of d electrons
almost cancels out this attraction and so the atomic and ionic radius does not vary very
much when comparing the transition elements to each other.

With smaller radii, the transition elements are denser than Ca.

Electrical conductivity of transition elements

Most of the transition elements are good conductors of electricity. Those with a single
outer s electron and a half filled or completely full d shell are especially good conductors.
Cu and Cr are better conductors than Ni and Mn as a result of this. Calcium is a good
conductor but too reactive to use in wires.
 The formation of coloured ions.
Coloured compounds appear coloured when they absorb energy that corresponds to
certain wavelengths of light in the visible spectrum. Aqueous Ti3+ ions appear purple
because they absorb light mostly in the green region of the spectrum. Most of the light
which passes through is from the violet, blue and red regions. So the solution appears
purple.

What causes the color?

Transition elements ions such as Ti3+, in solution are bonded to a definite number of
water molecules. Each water molecule forms a co-ordinate bond with the transition
element ion. These water molecules are called ligands and the resulting ion is called a
complex ion [Ti(H2O)6] 3+ .

- The 3d orbitals in an isolated transition element ion are degenerate (same average
energy).
- The presence of a ligand in a complex affects the electrons in the d orbitals of the
transition element ion. Orbitals close to the ligand are pushed to slightly higher energy
levels that those further away. The orbitals split into two groups.
 - When an electron moves from a d orbital of lower energy to a d orbital of higher energy,
light is absorbed in the visible region of the spectrum.
- The frequency of the light absorbed depends on the energy difference between the split d
levels. Different ligands split d energy levels by different amounts. So different ligands
may cause different colours to be absorbed.

READ AND DO FOR HOMEWORK

Physical properties:

 Ionisation energy across the transition elements

 Atomic and ionic radius across the transition elements
 Compare the melting point of Ca and the transition elements
 Compare the density of Ca and the transition elements
 Compare the atomic and ionic radius of Ca and the transition elements
 Compare the first ionisation energy of Ca and the transition elements
 Compare the electronegativity of Ca and the transition elements
 Compare the electrical conductivity of Ca and the transition elements

ANSWER THIS....

Formation of colour:

Copper’s most stable oxidation state is Cu2+ which is present in the following aq. compounds

[Cu(H2O)6]2+ : BLUE
[CuCl4]2- : YELLOW-GREEN

[Cu(NH3)4(H2O)2]2+ : DEEP BLUE

 Explain what causes the colour.

 Explain what causes the colour differences.

Coordination number.

-of a complex ion is the number of coordinate bonds a ligand forms (not the number of ligands)
with the central transition metal ion.

Monodentate ligands form one bond per ligand, e.g water, ammonia.

Bidentate ligands form two bonds per ligand, e.g. diaminoethane.

Hexadentate ligands form 6 bonds per ligand, e.g EDTA.

Ligand - an ion or molecule attached to a metal atom by coordinate bonding.

The Shapes of Complex Ions

The shape of a complex ion depends on:

- Its coordination number

- The type of ligand which bonds to the transition element ion

The shape of the complex cannot be predicted using VSEPR because the electrons in d orbitals
differ from those in s and p orbitals in their influence on structure.

CN =2

These complexes usually have a linear shape e.g. [Ag(NH3)2]+, CuCl2 –

CN = 4

These may be either square planar or tetrahedral in shape, although square planar is more
common (in many Ni (II), copper (II) and Pt (II) complexes). The tetrahedral form is found in
[CoCl4]2- ion and Ni(CO)4 molecule.
CN = 6

This is most common. It is octahedral. This shape is usually formed if the attaching ligand is
relatively small. They can also be formed using three bidentate ligands.

Coordination number of 2:

[Ag(NH3)2]+, [CuCl2]- Linear

Coordination number of 4:

[CoCl4]2- , [CuCl4]2-, Ni(CO)4 molecule, [NiCl4]2- Tetrahedral

[Ni(CN)4]2- , [Pt(NH3)4]2+ Square planar

Coordination number of 6:

[Cu(H2O)6]2+ , [Co(H2O)6]3+ , [Fe(CN)6]3- , Octahedral

(try drawing these)

HOMEWORK

Give one example of a hexdentate ligand.

What is it used for?

How do you think it works?

It is very effective in attaching to slightly larger metal ions like lead. This in turn takes them
out of the association with water in the aqueous blood system and allows them to be removed
with the help of the kidneys.

What is the name of the initial complex?

OBSERVATIONS:

What is the initial light blue ppt?

What do you think happened in the complex when xs ammonium hydroxide was added?

This complex will be redrawn to show changes

Can you name this new complex formed?

What is the charge on this new complex? Why?

RECAP

How many types of ligands are there? Give examples

What is ligand exchange? Why does it happen?

1.
Number of ligands: Number of ligands:

Coordination number: Coordination number:

2. This diagram below shows haem attached to haemoglobin in the blood. Using your
knowledge of ligand exchange explain how and why do you think carbon monoxide
poisoning occurs.

OXIDATION STATES OF VANADIUM

Vanadium is usually supplied as NH4VO3 (solid ammonium vanadate). When this is
acidified it becomes a part of a positive ion VO2 +.
+5 VO2+ Yellow

+4 VO2+ Blue

+3 V3+ Green

+2 V2+ Purple/mauve

0 V

The redox chemistry of V can be explained using an electrode potential chart. See page
162 of chem study guide.
Ligand exchange

If there is more than one ligand, they can compete for a transition metal cation. E.g. aq ammonia
contains two ligands: water and ammonia. The better the ligand is at competing for the transition
metal ion, the more stable is the complex formed.

Replacing water molecules by ammonia

Water molecules and ammonia molecules are very similar in size, and so
there is no change in co-ordination this time. Unfortunately, the reactions
aren't quite so straightforward to describe.

Ammonia solution can react with hexaaqua metal ions in two quite distinct
ways, because it can act as a base as well as a ligand.

If you add a small amount of ammonia solution you get precipitates of the
metal hydroxide - the ammonia is acting as a base. In some cases, these
precipitates redissolve when you add more ammonia to give solutions in
which a ligand exchange reaction has occurred.

In the diagrams below, both steps are shown, but we are only going to
consider the chemistry of the overall ligand exchange reaction. The
precipitates dissolve because of a complicated series of equilibrium shifts, and
we shan't worry about that for the moment.

Replacing the water in the hexaaquacopper(II) ion

This is a slightly untypical case, because only four of the six water molecules
get replaced to give the tetraamminediaquacopper(II) ion, [Cu(NH3)4(H2O)2]2+.
Notice that the four ammonias all lie in one plane, with the water molecules
above and below.

What you see in a test tube is:

The main equilibrium involved in the ligand exchange reaction is:

The colour of the deep blue complex is so strong that this reaction is used as
a sensitive test for copper(II) ions in solution. Even if you try to reverse the
change by adding large amounts of water to the equilibrium, the strength of
the deep blue (even highly diluted) always masks the pale blue of the aqua
ion.

Reference: http://www.chemguide.co.uk/inorganic/transition/features.html accessed April 2,

2016.

More Examples of ligand exchange

Replacing water with chloride ions

Replacing the water in the hexaaquacobalt(II) ion

If you add concentrated hydrochloric acid to a solution containing

hexaaquacobalt(II) ions (for example, cobalt(II) chloride solution), the solution
turns from its original pink colour to a dark rich blue. The six water molecules
are replaced by four chloride ions.
The reaction taking place is reversible.

Concentrated hydrochloric acid is used as the source of chloride ions because

it provides a very high concentration compared to what is possible with, say,
sodium chloride solution.

Replacing the water in the hexaaquacopper(II) ion

In terms of the chemistry, this is exactly the same as the last example - all that
differs are the colours. Unfortunately, these aren't quite so straightforward.
The colour of the tetrachlorocuprate(II) ion is almost always seen mixed with
that of the original hexaaqua ion.

What you normally see is:

The reaction taking place is reversible, and you get a mixture of colours due to
both of the complex ions.
You may find the colour of the tetrachlorocuprate(II) ion variously described as
olive-green or yellow.

Replacing the water in the hexaaquacobalt(II) ion

This time, all the water molecules get replaced.

The straw coloured solution formed changes colour very rapidly on standing to
a deep reddish brown. The hexaamminecobalt(II) ions are oxidised by the air
to hexaamminecobalt(III) ions. However, that is a quite separate reaction, and
isn't a part of the ligand exchange reaction.

Replacing the water in the hexaaquachromium(III) ion

Again, all the water molecules get replaced by ammonias. The difference this
time is that the reaction isn't so complete. The precipitate has to be left to
stand in the presence of excess concentrated ammonia solution for some time
in order to get the ammine complex.

Even so, you still get left with some unreacted precipitate.
A ligand exchange reaction in the test for iron(III) ions

This provides an extremely sensitive test for iron(III) ions in solution.

If you add thiocyanate ions, SCN-, (from, say, sodium or potassium or

ammonium thiocyanate solution) to a solution containing iron(III) ions, you get
an intense blood red solution containing the ion [Fe(SCN)(H2O)5]2+.

Also example 2 and 3 on page 165 of chem study guide.

Transition element compounds and redox

When compounds of transition elements are treated with suitable reagents, the oxidation state of
the transition element may change. E.g. manganite (VII), iron (III), dichromate (VI).
LAB EXPERIMENTS

Activity one: – Redox properties of transition elements

In this activity students will work in pairs and follow the instructions in the table. While students
wait for the required time they will move on to activity two.

Students will be asked to explain their observations during the oral evaluation at the end of the
experiments and must include their results on a poster using colour (paper or markers).

TEST OBSERVATION INFERENCE

 Add about 10 drops of

MnO4- 1 cm3 Fe2+ or until
the first colour change
 Add NaOH to resulting
solution

 Add 1 spatula full of Zn(s)

to a solution containing
Fe3+
 Leave for 15 mins
 Add NaOH to the resulting
solution

Activity two : Oxidation states of vanadium

Safety Precautions Ammonium metavanadate solution is highly toxic and corrosive to eyes, skin, and
other tissue. Wear chemical splash goggles.

 Pour the ammonium metavanadate solution into the boiling tube.

 Stopper the flask and gently shake the solution to reduce the vanadium (VO2 +) ions. (The
solution will gradually change color from green to blue to blue-green to dark green to
dark blue to purple.
What chemically happened to the Zn solid?

What happened to the V5+ ion?

Which are the oxidizing and reducing agents?

Experiment three : Ligand Exchange

The fume hood has to be utilized since conc HCl will be used for some of the reactions.

In the next demonstration conc HCl will be added to the copper sulphate solution.

What color are you predicting?

What is the shape of the initial ion?

What is the name of the initial ion?

Why is the name of the final ion?

What is the shape of the final ion?

Why did the shape of the final ion change?

In the next demonstration aq ammonia is added to the complex of [CuCl4]2-

[CuCl4]2- +4NH3 +2H2O ↔ [Cu(NH3)4(H2O)2]2+ + 4Cl-

Why did the shape change?

What is the charge on the new complex?

In the next demonstration HCl is added to the Co complex ion.

After the students take down the colour change for this reaction they have to prepare a chart for
the reaction and take a photo of it.
Add water to the complex formed

How can you explain the colour change back to pink?

Oxidation states of vanadium

Safety Precautions Ammonium metavanadate solution is highly toxic and corrosive

to eyes, skin, and other tissue.

 Pour the ammonium metavanadate solution into a boiling tube. Add a few
granules of Zn. Stopper the boiling tube and gently shake the solution to
reduce the vanadium. Record the colour changes.
Oxidation state of V Colour of solution

VO2+ Yellow

VO2+

V3+

V2+

Ligand Exchange

[CuCl4]2- +4NH3 +2H2O ↔ [Cu(NH3)4(H2O)2]2+ + 4Cl-