Practical Title: Student Name

BHEBE NKWANELE
Reg. No.
B1441641
. Course Code: 202
Course Description: INORGANIC CHEMISTRY II
Practical No: 5 : (d- Block elements- cobalt)
Practical Title: Reactions of cobalt chloride

Partner(s): : MUBVIGWI SITHABILE

Bhebhe Viola
B1441603
NdlovuSilibaziso
B1441751

B1441653

Aims
1. To study the preparation of the dextro- isomer of an octahedral chelate complex
and measure its optical activity.
Objectives
To become aware of the properties which enable a resolution of isomers to be made
To scale down a published experiment method
To study the chemical conditions that determine optical isomers.

Introduction

Isomers are molecules that have the same chemical formula but different structural formula.
Optical isomers are mirror images of one another. Optical isomerism is possible only in
molecules that do not contain improper rotational symmetry. The optical isomers are given the
designation D- and L- for the structural left and right handed isomers respectively. Only two
differences exist optical isomers: they will rotate polarized light in opposite directions and react
differently with other optical isomers. These properties allow for separation and analysis of
anantiomers.In this experiment tartaric acid which is chiral was used to separate one isomer from
another by crystalisation with tartaric acid. The reaction with tartaric acid is different for the two
optical isomers, hence one of the isomer was selectively precipitated, since
[(+)Co(en)3[(+)tart]CI has lower solubility than [(-)Co(en)3[(+)tart]CI
[(+)Co(en)3]3+(aq) +[ (+) tart](aq) Cl- +5H2O=[(+)Co(en)3[(+)tart]CI . 5H2O
The tatrate salt is then converted to the desired product , [(+)Co(en)3]I3.H2O by reaction with I(aq).The other isomer [(-)Co(en)3]I3.H2O is obtained by directly adding I-(aq) to a solution where
the other isomer was crystallized.
To evaluate the optical purity of the products, the rotation of the solutions of known
concentration and path length can be measured using a polarimeter(however this was not done
due to the unavailability of the polarimeter).Using the data, a specific rotation,[ ]D is calculated
for an optically active material
, [] D=/IC
, is the rotation angle of plane polarized light induced by the sample solution as measured using
a polarimeter
I, is the path length in dm
C, is the concentration in g of solute per ml of solution
Optically pure enantiomers have [] D of + and-890

Procedure
To the 1M solution of cobalt chloride, equal volume of concentrated sodium hydroxide was
added. The mixture formed a three layered precipitate (lilac at the top followed by purple
layer and a pink layer at the bottom).Sodium hydroxide was then added in excess, forming
a pink precipitate. This was followed by addition of hydrogen peroxide. To another portion
of 1M solution of cobalt chloride, ammonium hydroxide was added. To the green
precipitate formed excess ammonium hydroxide was added. The resulting solution was

divided into four parts, labeled A to D after adding equal volume of acetone. To each part
ammonium thiocyanate was added followed by a little acetone. To part A little ether was
added and the mixture was shaking thoroughly. To part B, a little mercuric chloride
solution was added and the mixture was boiled. To part C, a small amount of solid
ammonium fluoride was added. Part D was analysed using uv-vis spectroscopy and its
spectrum was compared to that of cobalt chloride solution. To the fourth part potassium
nitrite solution was added followed by acidification with dilute acetic acid. Little solid
potassium nitrite was added and the mixture was bubbled with air.

Preparation and Resolution of the Tris (ethyleneodiamine) cobalt (III) Iron

Preparation and resolution of the Tris (ethyleneodiamine) cobalt (iii) Iron
The tris (ethylencoiamine) cobalt iron is an example of a complex cation that exhibits optical
isomerism, and when it is prepared a racemic mixture of d and 1 forms obtained. In this
experiment these two antipodes are separated by fractional crystalisation of their tartrates.
Materials required:
Cobalt (II) sulphate
Concentrated hydrochloric acid
2mol /dm3 hydrochloric acid
Barium hydroxide
d-Tartaric acid
Activated charcoal
Concentrated aqueous ammonia
In a Buncher flask, 13.2cm3of ethylenediamic and 30cm3 water were mixed and cooled in an
ice bath.To this solution, 11cm3 concentrated hydrochloric acid was added,followed by addition
of cobalt sulphate (916.8g) dissolved in 30cm3 0f cold water and 2,5g of activated charcoal . A
rapid stream of air was drawn through the solution for 4hrs and then the pH was adjusted to 77.5 by the adding 2mol hydrochloric acid or ethylene diamine as required, the solution was then
heated on a stem bath for 20min.The solution was then cooled.Charcoal was then removed by
filtration.The removed charcoal was washed with 15cm3 hot water.The washed charcoal was
then added to the filtrate (which is a solution of tris (ethylene diamine) cobalt chloride sulphate).
Barium tartrate was prepared by mixing solutions of Barium hydroxide (18.8g) and d-tartaric
acid (9.0g) both compounds were dissolved in 20cm3 water at 90oC.The solution was then cooled
.The product was collected by filtration and washed on the filter with warm water. The solid
barium d-tartrate was added to the tris (ethylene diamine) Cobalt (lll) chloride sulphate solution
and the mixture was heated on a boiling water bath with constant stirring for 30minutes.The
resulting precipitate was removed ( barium sulphate) by filtration and washed in 10cm3 of hot
water. The washed charcoal was then added to the filtrate and the solution evaporated to 35cm3.
The solution was allowed to stand at room temperature for approximately 15h during which time
red crystals of (+) tris (ethylene diamine) cobalt (lll) chloride d-tertrate pentahydrate were
formed.The crystals were collected by filtration.The filtrate A which contains the (-) isomer was

kept. The crystals were washed with an equivolume mixture of ethanol and water (15cm3), then
absolute ethanol (10cm3) and dried in a vacuum.
The following isomer((+)Tris (ethylene diamine) cobalt (III) iodine hydrate) was prepared by
dissolving (+) tris (ethylene diamine) cobalt (III) chloride d-tartrate in 12cm3 hot water and
0,3cm3 of concentrated aqueous ammonia while stirring,this was followed by adding a solution
of sodium iodide(20.4g) dissolved in 8,5cm3 of hot water . The solution was cooled in an ice
bath. The product was collected by filtration on a Buchner funnel and washed on the filter with
an ice cold solution iodide (3.5g) in water (12cm3) and then acetone. The product was dried on
the filter by maintaining the vacuum.The product yield was then recorded.
Optical rotations of the three resolved complexes were not measured,due to unavailability of the
polarimeter.
Results and Discussion
Preparation of 1M cobalt chloride
1 mole CoCI2 =130g
1M
Color of Cobalt chloride is deep red
On adding concentrated sodium hydroxide to the cobalt chloride solution, three layers
formed with different colors. When excess sodium hydroxide was added a pink precipitate
was formed.
On adding hydrogen peroxide to the precipitate, effervescence was observed and a brown
precipitate was formed at the top and a choking smell characteristically of hydrogen was
produced.
On adding ammonium hydroxide, the layers formed (green precipitate at the top), on
adding excess ammonium hydroxide the precipitate layers dissolved giving a brown
solution, and this was accompanied by a violent reaction, with a gas being evolved with a
pungent smell (characteristic of ammonia)
On addition of acetone no color change was observed. After adding ammonium thiocynate
red-brown solution formed, this was followed by addition of acetate, a purple layer solution
formed which later dissolved on standing
This solution was then divided into four portions:
To the first portion, ether was added, a purple color formed and the top layer of the
solution was blue.

To the second portion of the solution, mercuric chloride solution was added and the
mixture was boiled. The mixture changed from a deep pink to a pink solution.
To the third part, sodium chloride was added, resulted in the solution which was violet
forming.
To the fourth part, ammonium nitrate solution which was acidified with dilute acetic acid,
the reaction was endothermic as the reaction vessel become colder. Brick-red solution
formed. Solid potassium nitrite was added, air was bubbled through the mixture, resulting
in a deep red precipitate
On dissolving potassium nitrite in Cobalt chloride an orange red precipitate was observed.
On acidifying with acetic acid, brown yellow precipitate was formed
Weighed mass of reactants
Mass of
2,008
Cobalt(III)Iodide
monohydrate/g
Mass of activated
2,503
charcoal/g
Mass of tartaric
5,004
acid/g
Mass of Barium
18,803
hydroxide/g
Mass of cobalt
9,1618
complex/g
Mass of D-tris2,009
ethyleneodiamine
cobalt(III)Iodide
monohydrate/g

2,008

2,008

2,503

2,503

5,0006

5,004

18,8002

18,803

9,1618

9,1618

2.0088

2,009

1. Illustrate how this complex can exist as optical isomers

2. Which chemical factors enable two such structurally similar compounds to be

isolated?
They rotate polarized light in opposite directions and they will react differently with other optical
isomers
3. Complex formation can bring about the stabilization of valence states transition
metals other than those commonly found? Comment on this statement with reference
to this experiment.