EXPERIMENT: 7

TITTLE:
SYNTHESIS OF PENTAAMINECHLOROCOBALT(III) CHLORIDE, [Co(NH3)5Cl]Cl2
Objective
To synthesize the pentaaminechlorocobalt(III) chloride complex.
Introduction
Complex compounds comprise of a large group of chemical compounds and is derived
from chemical elements, primarily from metals and in particular transition metals. Coordination
complexes exists in different forms, such as SO42-, MnO4-, [FeCN6]2-, etc.
Many metallic salts exists in the hydrated form, for instance, CoCl 2.6H2O and consists of
the complex ion such as [Co(H2O6]2+ here six water molecules act as the ligand bonding directly
to the central metal ion, Co2+, by coordinate bond through the donor atom from the ligand, that is,
the oxygen atom from the H2O ligand.
The ligands are arranged in an ordered manner around the central metal atom. Although
there are a number of stereochemistrys associated with these complexes but the most common
ones are those of coordination number 4 (with tetrahedral or square planar geometries) and 6
(with geometries that approximate an octahedron).
The objective of this experiment is to synthesize the chloropentaaminecobalt(III) chloride
complex. The scheme of the reactions for the preparation is given below:
2CoCl2.6H2O + 2NH4Cl + 8NH3 +H2O2 2[Co (NH3)5(H2O)] Cl3 + 12H2O
[Co (NH3)5(H2O)]Cl3 [Co (NH3)5Cl]Cl2 + H2O

Materials
Aqueous concentrated ammonia solution
Ammonium chloride
Cobalt(II) chloride 6-hydrate
Hydrogen peroxide solution
Concentrated hydrochloric acid

Procedure
1

In 7.5 mL aqueous concentrated ammonia solution, add 1.25g ammonium chloride.

With stirring, add 2.5g cobalt (II) chloride 6-hydrate in small portion. Do not add the next
portion until the added portion has dissolved. A yellow precipitate will form easily.

To the slurry above, with stirring, add slowly hydrogen peroxide solution (2.0 mL, 30 %
v/v). A strong reaction will occur.

After the reaction has stopper add slowly 7.5 mL concentrated hydrochloric acid solution
to the red aquapentaamine solution.

Heat this product on a hot water bath for 20 min. Filter off the product by vacuum suction
and washing with cold water.

Resuts:
Mass of ammonium chloride = 1.2449g
Mass of cobalt (II) chloride 6-hydrate = 2.5006g
Mass of [Co(NH3)5Cl]Cl2 = 0.3988g
Molar mass of ammonium chloride = 53.49 g/mol
Molar mass of cobalt (II) chloride 6-hydrate =237.93 g/mol
Discussion:
1- Synthesis of [Co (NH3)5Cl] Cl2:
The Co (II) was oxidized to Co (III) by using an oxidizing agent H2O2 that leads to fast redox
reaction and can easily break the single bond. Also, it was added to generate a large excess of
the NH3 ligands. The equations below show the half reactions (oxidation and reduction) in the
addition of H2O2.

2[Co 2 ( aq) Co 3 ( aq) e ]

2e 2 H ( aq) H 2 O2 ( aq) 2 H 2 O( aq )
______________________________________
2Co 2 ( aq) 2 H ( aq) H 2 O2 ( aq) 2Co 3 2 H 2 O( l )

The red color of the solution was appeared after adding H2O2 due to the aqua. The following
equation shows the overall reaction after the addition of H2O2 :
2[Co 2 ( aq) NH 4

( aq )

4 NH 3 ( aq ) 1 / 2 H 2 O( aq) [Co( NH 3 ) 5 H 2 O]( aq ) ]

[Co( NH 3 ) 5 H 2O ]3 ( s ) 3Cl ( aq ) [Co( NH 3 ) 5 Cl ]Cl2( s ) H 2O(l )

In addition, to replace
an aqua ligand from the complex HCl(aq) was added with chloro ligands as shown in this
equation:

The Cl- ions were responsible for the purple color of solution. It acts as a counter ion as well to
balance the charge of the complex ion. So, the overall reaction of the final product was:

2CoCl2 6 H 2 O( s ) 2 NH 4 Cl( s ) 8 NH 3 ( aq ) H 2 O2 ( aq ) 2[Co( NH 3 ) 5 Cl ]Cl2 ( aq ) 14 H 2 O(l )

The complex was deposited as a purple solid in 15.15% yield. It is clear that that the yield was so
low because of the losing of some product during filtration of the product, or when transferring
or weighting the starting material.
From the geometric structure of the final product below, it seems that the coordination number
which is the secondary valence of the central atom is 6 and the primary valence is 3. Also, the
valence of NH3 and Cl- both equal to 1. It clear that the complex is octahedral with 6 ligands ( 5
NH3, 1 Cl- ) and 2 Cl- as counter ions. Therefore the total ions from Blomstrand Chain Formula
of the complex should be 3 (1 cation, 2 anions).But when I measured the electrical conductivity
of the final product, the specific conductance was 0.37 which gives (370 -1cm-1mol-1) molar
conductivities that means the compound should has 4 ions and that is not true. The reason for
that result was due to the ionized water which was used to prepare the 0.001 M solution of the
compound so, the specific conductance become 0.28 (0.37-0.09) which gives (280 -1cm-1mol-1)
as the molar conductivity that the corresponding number of ions equal to 3.
The 5 d-orbitals in an atom have certain spatial arrangements, just as the ligands surrounding a
complex have certain spatial arrangements. What allows a ligand to be a ligand are lone pairs of
electrons. If a ligand is closely situated to an orbital, repulsion between the electrons in the
orbital and those in the ligand occur. This repulsion makes that orbital effectively a higher energy
state than the other orbitals. The basic structure the model deals with is an octahedral complex
with uniform ligands although it can account for linear, square planar, and tetrahedral complexes
with mixed ligands. Even like this, two of the five orbitals are higher energy than the others.
Different ligands cause different levels of repulsion and thus alter the size of the gap in energy
between the two possible energy levels. When light strikes a complex, an electron can absorb a
photon with just enough energy to carry it to the higher energy orbitals. Since photon energy is

dependent on the wavelength, and wavelength is perceived as colour, different ligands cause
different colours to be absorbed, resulting in the complementary colours to the absorbed colour
being perceived as the colour of the complex. For example, hexaaquacopper (II) is the familiar
blue of aqueous Cu (II). In order to be blue, the complex must absorb wavelengths in the
yellow/orange/red region. These are shorter wavelengths and thus lower energy. The "splitting"
between the orbitals must be fairly small and H2O ligands produce a fairly weak "crystal field" If
we add a chloride, we have a colour shift to green. Green is allowing blues, greens, and yellows
to pass and only absorbing the very low energy reds and oranges. Cl- produces an even weaker
crystal field than H2O.
In this experiment, there are some precaution steps needed to be taken. The solution should be
mixed properly to make sure the result is correct. The mixture must be constantly stirred. The
cobalt (II) chloride 6-hydrate was added in small portion due to it cannot dissolve easily which
needed to pour slowly. The product should in slightly incline way and wash with cold water to let
the product can easily come down with water.

QUESTIONS
1 Draw the structure of the complex.

H3N

Cl

NH3

Co
H3N

Cl2

NH3 NH3

Figure 1: the structure of [Co (NH3)5Cl] Cl2

2

Describe the synthesis of the complex.

The ammonia and chloride ligands of these complexes use lone pairs of electrons to form
bonds with the cobalt cation. The coordination number for the cobalt in both products is six
and these cations are octahedral, as predicted by VSEPR theory. The cobalt ion ends up
having a charge of 3+; each chloride ion is 1-, and the ammonia ligands are neutral, so
[Co(NH3)6] has a net 3+ charge and [Co(NH3)5Cl] has a net 2+ charge.
3

Based on your understanding, why is it that the crystals obtained have to be washed
with cold water?

The crystals that obtained have to be washed with cold water is to prevent the loss of the product
by dissolving and preserving the solid crystals before vacuum filtration. This is because cold

water can reduce the kinetic energy of the crystals molecule effectively instead of warm water.
When kinetic energy reduced, the molecules will not collide effectively with other molecules.
The crystals formed might be dissolve in the water again if hot water is used and this will affect
the result and the result will not be accurate.
4

What are the impurities that may be present in the product?

Cobalt oxide, CoO,CoCl2.6H2O and NH4Cl

5

Assuming that the reactions go to completion, how many moles of the product are
expected?

2CoCl2.6H2O + 2NH4Cl + 8NH3 +H2O2 2[Co (NH3)5(H2O)] Cl3 + 12H2O

[Co (NH3)5(H2O)]Cl3 [Co (NH3)5Cl]Cl2 + H2O
2 mol of CoCl2.6H2O = 2 mol of [Co (NH3)5(H2O)] Cl3
no of mole of CoCl2.6H2O = no of mole of [Co (NH3)5(H2O)] Cl3
= no of mole of [Co (NH3)5Cl]Cl2
2 mol of [Co (NH3)5Cl]Cl2 are expected when the reactions go to completion
6

Calculate the percentage yield of your product.

mass
molar mass

no of moles of CoCl2.6H2O =
=

2.5006 g
237.93 g/mol

=0.01051mol
Theoretical mass of [Co (NH3)5Cl]Cl2 = 0.01051mol x 250.4448g/mol
= 2.6322 g
Percentage yield =
=

Massof actual yield

Mass of theoritical yield
0.3988 g
2.6322 g

x100%

x 100%

=15.15%
7

Suggest how the percentage yield can be improved in the experiment above.

The percentage yield can be improved if the experiment is repeated twice. Furthermore, Increase
the temperature of water bath. Add more HCl to expel all the CO2, rinse the compound with 2 to
3mL of ethanol repeatedly while filtering. Set the substance into an oven at 120 degrees
Fahrenheit to dry and let the moisture out for accurate weighing. Apart from that, the product
need to wait until it is completely dry before it was weighed to improved the percentage yield.
The cobalt (II) chloride 6-hydrate should be added slowly, after the previous added portion has
dissolved in the mixture so that the reaction is complete and all the cobalt (II) chloride 6-hydrate
is dissolved in the solution to improve the percentage yield. After heating the product and wait
for the product to be cooled, a longer time can be spent so that more precipitate can be formed to
improve the percentage yield.

CONCLUSION:
The cobalt (II) chloride 6-hydrate react with ammonium chloride, ammonia and hydrogen oxide
form pentaaminechlorocobalt(III) chloride. The percentage yield of the product is 15.15% due to
some error occur.
References:
Cobalt (II) chloride [Online] Available at:
http://www.rsc.org/learn-chemistry/resource/rws00022708/cobalt-ii-chloride
[Accessed 10 April 2015].
Subject: Cobalt (III) Ammine/Chloro complexes and Crystal Field Theory {Online} Available at:
http://www.sciencemadness.org/talk/viewthread.php?tid=10368 [Accessed 10 April 2015]

NAME

: BERNARD CHEONG JIA CHOON

ID

: 1406645

NAME OF PARTNER

: GAN TE QUAN
: PAN WAI SENG
: TANG YI ZHANG
: KAVISHA A/P SUNDANRAJ

PRACTICAL GROUP

: P2

EXPERIMENT NO.

:7

EXPERIMENT TITLE

: SYNTHESIS OF
PENTAAMMINECHLOROCOBALT(III)
CHLORIDE, [Co(NH3)5Cl]Cl2

EXPERIMENT DATE

: 01/04/2015

SUBMISSION DATE

: 13/04/2015

LECTURER NAME

: Dr. LIM TUCK MENG