Lab Report

Experiment: Formation of color complexes of Cobalt

Introduction:
The d-orbitals of a free transition metal atom or ion are degenerate (all have the same energy.)
However, when transition metals form coordination complexes, the d-orbitals of the metal interact
with the electron cloud of the ligands in such a manner that the d-orbitals become non-degenerate
(not all having the same energy.) The way in which the orbitals are split into different energy levels
is dependent on the geometry of the complex. When the d-level is not completely filled, it is
possible to promote and electron from a lower energy d-orbital to a higher energy d-orbital by
absorption of a photon of electromagnetic radiation having an appropriate energy. Electromagnetic
radiations in the visible region of the spectrum often possess the appropriate energy for such
transitions. This experiment is designed to study the behavior of cobalt complexes. The oxidation
state of cobalt is changed in different complexes by changing the nature and concentration of
ligand.
Physical properties of Cobalt:
Atomic Number 27 Mass 58.933195 g/mol
Group 9 Period 4
Electron Configuration [Ar] 4s2 3d7 Density 8.9 g.cm-3
Melting Point 1495 degrees C Boiling Point 2870 degrees

Chemical Properties of Cobalt:

Cobalt is reactive element. It combines with oxygen in the air, but does not catch on fire and burn
unless it is in powder form. Cobalt has the ability to react with most acids to produce hydrogen
gas. However cobalt does not react with water that is at room temperature. The simplest ion that
cobalt forms in solution is the pink hexaaquacobalt(II) ion - [Co(H2O)6]2+. Cobalt(II) chloride is
often used in humidity indicators because in dry form it is blue and when hydrated it is pink. The
radioactive isotope of cobalt, Co-60, is used in portable "x-ray" devices. It actually produces
gamma rays which can be used to detect internal flaws in metal in much the same way as x-rays
by producing a shadowy image on film. Co-60 is also used in cancer treatment.
Color Complexes of Cobalt:

The majority of Co(II) and Co(III) complexes are brightly colored. Alfred Werner, who founded
and developed the field of complex chemistry, originally named compounds based on their color
rather than on their chemical composition, as the following short list illustrates

Structural representation Oxidn. Number Werner Name (color)

Present In 19th Century

[Co(NH3)6]Cl3 CoCl3.6NH3 Co(III) Luteocobalticchloride (yellow)

[Co(NH3)5H2O]Cl3 CoCl3.5NH3.H2O Co(III) Roseocobaltic chloride (red)
[Co(NH3)5Cl]Cl2 CoCl3.5NH3 Co(III) Purpurocobaltic chloride (purple)

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 Lab Report

Apparatus:

Test tubes, Pipette (10 mL), Pipette filler, Watch glass, Glass rod, volumetric flask (50 mL), Water
bath.

Chemicals:

 CoCl2.6H2O, cobaltous chloride hexahydrate (0.1M)

 NH4OH, ammonium hydroxide (6 M, 15 M)
 H2O2, hydrogen peroxide (30%)
 NaOH, sodium hydroxide (3 M)
 HCl, hydrochloric acid (10 M)

Procedure:

1. Take 3 mL of cobalt soln. + 6 M NH4OH (few drops)3 mL of cobalt soln. color changes
from pink to blue.
2. Take 3 ml of cobalt solution and 15 M NH4OH and note the color changes.
3. Take 3 mL of cobalt soln. + 15 M NH4OH in excess + 1 mL of H2O2 and note the color
changes.
4. 4 mL of cobalt soln. + 3 M NaOH dropwise + heat solution and note the color changes.
5. 3 mL of cobalt soln. + 10 M HCl (excess) + dilute with H2O and note the color changes.

Observations

Test no. Reagents Observation Color of ppts.

1 3 mL of cobalt soln. + 6 M NH4OH Color changes Blue
(few drops) from pink to blue
2 (a) 3 mL of cobalt soln. + 15 M NH4OH Pink to Blue Blue

(b) 3 mL of cobalt soln. + 15 M NH4OH Green to Brown Brown

in excess + 1 mL of H2O2

3 4 mL of cobalt soln. + 3 M NaOH Pink to violet. Brown

dropwise + heat Violet to brown
4 3 mL of cobalt soln. + 10 M HCl Pink to light pink light pink
(excess) + dilute with H2O

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Chemical Reactions
1. 3 mL of cobalt soln. + 6 M NH4OH & 3 mL of cobalt soln. + 15 M NH4OH
The ammonia acts as both a base and a ligand. With a small amount of ammonia, hydrogen ions
are pulled off the hexaaqua ion exactly as in the hydroxide ion case to give the same neutral
complex.

That precipitate dissolves if you add an excess of ammonia. The ammonia replaces water as a
ligand to give hexaamminecobalt(II) ions.

Structure:

Hexaamminecobalt(II)

2. 3 mL of cobalt soln. + 15 M NH4OH in excess + 1 mL of H2O2

The reaction with ammonia solution followed by hydrogen peroxide produces the same dark
reddish-brown solution as before - only faster. The equation for the oxidation of the ammine
complex is:

3. 4 mL of cobalt soln. + 3 M NaOH dropwise + heat

Colored precipitate of the cobalt(II) hydroxide complex is obtained when you add the sodium
hydroxide solution. Addition of hydrogen peroxide produces lots of bubbles of oxygen and a
dark chocolate brown precipitate.
The final precipitate contains cobalt in the +3 oxidation state.

4. 3 mL of cobalt soln. + 10 M HCl (excess) + dilute with H2O

If concentrated hydrochloric acid is added to a solution containing hexaaquacobalt(II) ions, the
solution turns from its original pink color to a rich blue. The six water molecules are replaced by
four chloride ions. The reaction taking place is reversible.

If water is added to the blue solution, it returns to the pink color.

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Result:
Different color of cobalt appears on reaction with different reagent. Different color changes are
observed.

Discussion:
Transition metal ions are not colored on their own - it is only when they become complex ions
that they become colored. Accordingly, there is now a set of 3 orbitals and a set of 2 orbitals.
These sets are at different energy levels - the 3-orbital set is at a lower energy level than the 2-
orbital set. Hence, a specific amount of energy is needed for an electron to move from the lower
orbitals to the higher orbitals.
The energy required corresponds to a specific frequency of light
ΔE = hf
Hence, when white light is shone onto the complex ion, certain frequencies of light are absorbed
(which promotes an electron to a ‘higher’ orbital).
Any light which is not absorbed is the color of the complex ion as the non-absorbed light is
reflected back into our eyes. For example, if the color of the complex ion is blue - this means that
red light is absorbed and that blue light is reflected. It is helpful to look at the visible spectrum of
light for this .In essence, the color that we see consists of the frequencies of light which are not
absorbed.
Finally, different ligands interfere with the ion’s orbitals differently and thus, cause different
splitting of the d-orbitals. Therefore, different frequencies of light are absorbed and this leads to
different colors.
For example, Cu2+ in water is pale blue (the water molecules are the ligands) but when ammonia
is added, the complex ion turns a royal blue color.