Experiment 10

COLOURS IN CHEMISTRY (A)

Introduction:

Colour is a distinctive property of many chemical compounds. If a compound absorbs radiation

from the visible part of the electromagnetic spectrum, then the colour observed for the
compound is the complementary colour to that absorbed. In transition metal complexes, often
when radiation is absorbed an electron is excited to a higher energy state (t 2g  eg) and the
frequency of the radiation absorbed can be measured and used to calculate electron orbital
energies, and crystal field splitting energy, o.

- - eg

- - - - - o
degenerate d
orbitals

- - - t2g

Different ligand systems i.e spectrochemical series and stereochemistries give rise to different
o values and so to differently coloured complexes. For example,CoCl2 in aqueous solution
contains (d7, octahedral) [Co(H2O)6]2+ which is pale pink, whereas in ethanol solution the dark
blue colour suggests tetrahedral stereochemistry arising from species such as [CoCl4]2- or
[CoCl2(EtOH)6]2+ octahedral species. The equilibrium [Co(H2O)6]2+  [CoCl4]2- is easily
traced by examination of the colour of the solution.

Pre-lab Questions:
1. What wavelengths correspond to the visible region of the electromagnetic spectrum (in
nm)?
2. If the energy absorbed by the species falls outside the visible region, what colour will the
compound appear to be?
3. What is meant by complementary colour? Explain using the colour wheel.
4. A cobalt complex absorbs strongly at 600 nm, what colour would you expect it to appear?

Safety Recommendation:
Ammonia (NH3): This compound is pungent, non breathable gas. It is harmful if swallowed,
inhaled, or absorbed through the skin.

Cobalt(II) chloride hexahydrate: This compound is harmful if swallowed, inhaled,

or absorbed through the skin.

Hydrogen Chloride: Concentrated HCl is very corrosive.

Experimental:

1. Colour changes

Draw up a table in which to record:

o Colours of starting materials
o Colours of products
o Equation(s)
o The species producing the colours

Note and record all the colour changes.

a. Dissolve (approx. 0.1 g) of Cobalt(II)chloride hexahydrate (CoCl2.6H2O), in a minimum

amount of ethanol and note the colour. Add water drop wise and observe.

b. Dissolve (approx. 0.1 g) CoCl2.6H2O in a minimum amount of water and to the solution
i. add conc. HCl dropwise
ii. pour the solution from (i) into excess water.

c. Dissolve (approx.0.1 g) of NiCl2.6H2O in water. To separate samples (in the fume

cupboard) add
i. conc. NH3
ii. 1,2-diaminoethane(en) dropwise with shaking until no further colour change
is observed.

d. Dissolve (approx. 0.5 g) of CuCl2.2H2O in water. To three separate samples add dropwise:
i. Conc. NH3
ii. Ethylenediamine (en)
iii. Conc. HCl

2. Oxidation States of Vanadium:

2a. Preparation of a standard solution of Vanadium(V):

Safety Recommendations:
Sodium hydroxide: This is harmful if swallowed, inhaled, or absorbed through the skin.
It is extremely caustic, especially on wet surfaces.

Ammonium metavanadate: This compound is harmful if swallowed, inhaled, or

absorbed through the skin. Avoid breathing the dust.

Dissolve an accurately weighed amount, about 2.0 g, of ammonium metavanadate (MW 117.0
g/mol) in about 50 cm3 of sodium hydroxide solution (1 M). While stirring this solution
vigorously, add rapidly about 80 cm3 of dilute sulphuric acid (4 M). Transfer this solution
quantitatively to a 250 cm3 volumetric flask and make up to the mark with distilled water.
Calculate the molarity of this solution.
2b. Reduction of Vanadium (V) with Sulphite:
(Do this in duplicate and experiment must be carried out in the fume cupboard)

Theory:

The experiment is carried out in two steps and in both steps a redox reaction occurs. Firstly,
Vanadium with an oxidation number of 5+ is reduced to an unknown oxidation number, say
n+ by sulphite. Sulphite in turn is oxidised to sulphur dioxide. Secondly, the reduced
Vanadium solution of n+ oxidation state is titrated with KMnO4 and is oxidised back to 5+ and
KMnO4 is reduced to Mn2+.

Safety Recommendations:
Potassium permanganate: This compound is a powerful oxidising agent and should be handled
with care. It is harmful if swallowed, inhaled, or absorbed through the skin. It is extremely
destructive to the mucous membranes and skin.
Sodium Sulphite: This compound is harmful if swallowed, inhaled or absorbed through the
skin.

Sulphuric Acid: The acid is extremely corrosive. Strong oxidising and dehydrating agent.

Experimental:

1. Pipette out 25.0 cm3 of the standard vanadium (V) solution into each of two 250 cm3 conical
flasks. To each add about 5 cm3 dilute sulphuric acid and about 0.25 g sodium sulphite.
Gently, boil the solution until all excess of sulphur dioxide is removed. Check by moist
dichromate paper.
2. Titrate the still hot solution (should be maintained close to 60 0C) with the standard KMnO4
solution provided. The end point is given by the first permanent appearance (pinkish
colour) of the permanganate (first colour after yellow).

Analysis:

Calculate the number of moles of vanadium taken in the 25 cm3 aliquot. Take the mean of the
two permanganate titres, and calculate the mean number of moles of permanganate required.
From the half-equation for oxidation by permanganate, calculate the number of moles of
electrons transferred per mole of MnO4-.

Calculate the ratio: Moles of electrons transferred/moles of vanadium taken.

This will give the change in oxidation state of vanadium. Hence, deduce the oxidation state of
the reduced vanadium (n+) solution.

Questions:

1. What is the purpose of adding sulphuric acid to the solution in 1?

2. Suggest reasons why your calculated oxidation state may deviate from being an exact
integral number (i.e. discuss sources of error).