Title: Separation of Complex Cations of Chromium(III) by Ion Exchange Chromatography.

Aim - Separation of Cr(III) complexes

Aqueous solutions of the complexes trans-[CrCl2(H2O)4]Cl, [CrCl(H2O)5]Cl2 and [Cr(H2O)6]Cl3 were
isolated in a pure state based on their different affinities for a cationic exchange resin which results
from their differing cationic charges. The cations were identified using UV-Visible
spectrophotometry, and this also allowed the crystal field strengths of the two ligands involved to be
compared.
Procedure:
1. Preparation of an ion exchange column
A burette was half-filled with deionized water and 1cm in height of sand was poured in. A slurry
of Dowex 50W-X8 (20-50 U.S. mesh) cation exchange resin in deionised water was poured in
through a funnel, until a final resin height of approximately 15 cm was achieved. Water was
allowed to pass through the resin until the eluent was colourless, the the water level was
lowered so that it coincides with the top of the resin.
2. Preparation of perchloric acid solutions
Solutions of (HClO4), each of 200 cm3, with concentrations 0.1 mol dm-3 and 1.0 mol dm-3 and
that with concentration 3.0 mol dm-3, were prepared by the laboratory staff and used to elute
the desired complexes.
3. Preparation of chromium solutions
100 cm3 of [CrCl2(H2O)4]+ solution (0.42 mol dm-3) was prepared by dissolving commercial
CrCl3.6H2O in 100 cm3 of aqueous HClO4 (0.002 mol dm3) to be used in portions throughout the
experiment.
4. Separation of trans-[CrCl2(H2O)4]+
5 cm3 of the [CrCl2(H2O)4]+ solution (0.42 mol dm-3) was poured carefully onto the top of the
cation exchange resin previously prepared. The solution was allowed to drain through the
column, one drop at a time, until the solution and resin levels were the same. HClO4 (0.1 mol
dm3) was added to the column and the [CrCl2(H2O)4]+ was eluted using a flow-rate of
approximately 1 drop per second. Approximately 5 cm3 of the [CrCl2(H2O)4]+ solution was used
for the recording of its UV-Visible spectrum. Only the portion of the eluent with a relatively
intense colour was collected.
The spectrum of trans-[CrCl2(H2O)4]+ in the wavelength range of 350 to 750 nm was recorded on
the spectrophotometer provided, using cells of 1 cm path length.
5. Another column was prepared using the same procedure as in 1.
6. Separation of [CrCl(H2O)5]2+

A flask containing 10 cm3 of the [CrCl2(H2O)4]+ solution (0.42 mol dm-3) was swirled in a water
bath at 50-550C for about 2 minutes. 10 cm3 of water was added immediately and poured
carefully on to the top of a fresh column. After draining the solution to the resin level, the
column was washed with HCIO4 (0.1 mol dm3) until the un-reacted [CrCl2(H2O)4]+ had been
eluted. The desired complex, which had been held at the top of the column as a dark band, was
then eluted with HClO4 (1.0 mol dm3). Approximately 5 cm3 of the intensely coloured fraction
was collected and the UV-Visible spectrum (350 to 750 nm) was measured as soon as possible
after collection.
7. Another column was prepared using the same procedure as in 1.
8. Separation of [Cr(H2O)6]3+
10 cm3 of the [CrCl2(H2O)4]+ solution (0.42 mol dm3) was diluted with 10 cm3 of distilled water and
boiled for 5 minutes. To the resulting solution of [Cr(H2O)6]3+, an additional 10 cm3 of water was
added and cooled to room temperature. All of this solution was added carefully to the column
and drained until the solution level reached that of the resin. The column was first rinsed with
HCIO4 (1.0 mol dm3) to remove any un-reacted mono-cation and di-cation, then the complex
[Cr(H2O)6]3+ with HClO4 (3.0 mol dm-3) was eluted. Approximately 5 cm3 of an intensely coloured
portion of the eluted [Cr(H2O)6]3+ solution was collected and its UV-Visible spectrum (350 to 750
nm) recorded.
Results:
Complexes

trans-[CrCl2(H2O)4]+

[CrCl(H2O)5]2+

[Cr(H2O)6]3+

Peak 1

Peak 2

Peak 1

Peak 2

Peak 1

Peak 2

Absorbance

0.638

0.644

0.716

0.571

0.543

0.462

Wavelength
(nm)

446

632

432

610

410

580

E=

6.626 1034 2 / 299000000 /

580109

= 3.416 x 10-19 J

oct for [Cr(H2O)6]3+ is 3.416 x 10-19 J

Discussion:
In a cation exchange system, the cation with three positive charges will bind first and the cations
with a smaller charge will bind in lower layers. If all three of the above chromium complexes are
present, the order of binding will be:
Cr(H2O)63+> Cr(H2O)5Cl2+> Cr(H2O)4Cl2+

The larger the acidity of the solution the more is the equilibrium shifted to the right. In the present
case, when an acid of a certain concentration is passed through a column of the resin with the three
different cations attached to the negative sites of the resin, the Cr(H2O)4Cl2+ can be liberated to the
solution, while the two other cations stick to it. This leaves a solution with only Cr(H2O)4Cl2+ ions and
the two other cations remaining on the column in two layers. Now, if the acid concentration is raised
it is Cr(H2O)5Cl2+, which is the next cation to lose the competition to the protons for the negative
sites on the resin. Cr(H2O)5Cl2+will accordingly be liberated to the acid solution. The
hexaaquachromium(III) ion with its three charges will only be ousted by protons if the acid
concentration is raised further.

Conclusion:

oct for [Cr(H2O)6]3+ is 3.416 x 10-19 J. The crystal field strength of H20 ligand is higher than of
the Cl- ligand.