An Evaluation of The Spectrochemical Series:

The Preparation and Spectroscopy of Chromium(III) Complexes

The d orbitals of a metal ion in an octahedral crystal field (surrounded by an octahedral

array of ligands) are split into a higher energy eg set and a lower energy t2g. The energy
difference between the upper and lower energy levels is designated as ∆o or, in the older
literature, as 10Dq. The degree of splitting of the d orbitals and hence the magnitude of
∆o depends on several factors, including the charge on the metal, the size of the metal,
and the nature of the ligand. The situation is simplified considerably by considering a
series of complexes with the same metal in a given oxidation state. The only major
variable, in this case, is the ligands bonded to the metal. From a large number of studies
it is known that ligands can be arranged in a sequence according to their ability to cause
d-orbital splitting. This series is known as the spectrochemical series:

halides < OH– < C2O42– < H2O < NCS– < py < NH3 < en < phen < NO2– < CN– < CO

The magnitude of ∆o increases by a factor of about 2 as one moves from halide to CN– in
the spectrochemical series. Carbon monoxide has the strongest ligand field of all the
common ligands.

The objective of this experiment is to quantify ∆o for a series of Cr(III) complexes by

electronic absorption spectroscopy. Cr(III) compounds are d3 and their electronic
spectral characteristics are reasonably easy to interpret. This is normally done through a
Tanabe-Sugano diagram where energy is plotted against the magnitude of the crystal field
splitting parameter for a d3 ion, Figure 1. The lowest energy state is designated 4A2 and
is the ground state. Optical excitation to other quartet excited states is allowed by
4T 2A
1g 2g
80

70 2A
1g
4T
60 1g

50 4T
2g
E/B

40
2F
2T
2g
30
2T
1g
20 2E
2G g
4P
10
4F
4A
0 2g
0 10 20 30 40 50
∆o/B
Figure 1
selection rules. The states in order of ascending energy are labeled 4T2 (two electrons in
the t2g and one in the eg), 4T1, and another 4T1 (one electron in the t2g and two in the eg).
The energy separation between the two lowest energy levels, 4A2 and 4T2 is ∆o. This
absorption band will be the one at the longest wavelength (lowest energy) in the
spectrum.

Hazards

Chromium(III) chloride hexahydrate (CAS No. 10060-12-5): Chromium compounds

are considered mildly toxic. ORL-RAT LD50: 1790 mg/kg. Chromium(II) compounds
in general, have little toxicity. Certain compounds are harmful if inhaled or swallowed.

Chromium(III) nitrate nonahydrate (CAS No. 7789-02-8): ORL-RAT LD50: 3250

mg/kg.

Methanol (CAS No. 67-56-1): This liquid can be fatal if swallowed and is harmful if
inhaled or absorbed through the skin. ORL-HMN LDLo: 143 mg/kg, ORLRAT LF50:
5628 mg/kg. The compound is flammable and highly volatile.

Zinc (CAS No. 7440-66-6): Zinc is not generally considered to be a dangerous material,
however the usual safety precautions should be taken.

Ethylenediamine (CAS No. 107-15-3): This compound is harmful if swallowed,

inhaled, or absorbed through the skin. ORL-RAT LD50: 500 mg/kg. It should be used
only in the hood.

2,4-Pentanedione (CAS No. 123-54-6): Also known as acetylacetone. This compound

is a mild irritant to the skin and mucous membranes. It is a flammable liquid. ORL-RAT
LD50: 590 mg/kg.

Urea (CAS No. 57-13-6): Urea is not generally considered dangerous and is classified as
a diuretic. ORL-RAT LD50: 8471 mg/kg.

Potassium dichromate (CAS No. 7778-50-9): Chromium(VI) compounds are generally

more toxic than chromium(III) compounds. May be fatal if absorbed through the skin, if
swallowed or inhaled. Contains chromium(VI), a known cancer hazard. Allergen. Skin
eye and respiratory irritant. ORL-RAT LD50 177 mg/kg.

Potassium oxalate monohydrate (CAS No: 6487-48-5): Corrosive - causes burns.

Very destructive of mucous membranes. Toxicology not fully investigated.

Oxalic acid dihydrate (CAS No: 6153-56-6): Harmful if swallowed, inhaled or

absorbed through skin. Corrosive - causes burns. Very destructive of mucous
membranes. ORL-RAT LD50 7500 mg/kg.
Experimental Procedure.

A. Preparation of Tris(2,4-pentanedionate)chromium(III)

Dissolve 130 mg of CrCl3·6H2O in 2.0 mL of distilled water with stirring. Add 500 mg
of urea and 400 µL of 2,4-pentanedione. Heat the mixture to just below boiling with
stirring for one hour. As the urea releases ammonia and the solution becomes basic, deep
maroon crystals will begin to form. After one hour, cool the flask to room temperature.
Collect the crystals by suction filtration. Wash the crystals with three 20-mL portions of
distilled water. Dry the product, determine the percentage yield, and transfer to a labeled
vial.

B. Preparation of Tris(ethylenediamine)chromium(III) Chloride Trihydrate

Reflux 100 mg of mossy, granular zinc, 266 mg of CrCl3·6H2O, 1 mL of

ethylenediamine, and 1 mL of methanol with stirring for one hour. Cool the solution to
room temperature.

The solution is then cooled to room temperature and the yellow product collected on a
sintered glass. The filtered product is then washed with acetone/methanol mixture until
the washings are colorless. Unreacted zinc is separated by dissolving the product using a
minimal amount of distilled water. The yellow solid is precipitated from the filtrate with
acetone. Filter, rinse with acetone and ether and allow the product to dry. Determine the
percentage yield and transfer to a labeled vial.

C. Preparation of Potassium Tris(oxalato)chromate(III) Trihydrate

In a 50-mL beaker, add 0.46 g of K2C2O4·H2O and 1.10 g of H2C2O4·2H2O to 20.0 mL of

distilled water and stir vigorously. Add 0.38 g of K2Cr2O7 in one portion. Stir the
mixture (white suspension in yellow-orange solution) for about 45 min or until it
becomes a dark olive solution with no undissolved solids. Continue stirring and add an
equal volume (~20 mL) of ethanol. When the complex has oiled out, decant off the
mostly colorless solution and discard. Triturate the oily solid with ether to isolate a
powdery dark blue-green solid. Collect the complex by suction filtration and wash with
three 10-mL portions of ether. Allow the solid to dry under vacuo. Determine the
percentage yield, and transfer to a labeled vial.

D. Preparation of Hexakis(urea)chromium(III) Chloride

CrCl3·6H2O (2.7 g) and urea (3.6 g) are dissolved in 10 mL of distilled water and a few
drops of 3 M HCl is added. The solution is heated on a steam bath until a crystalline
crust forms. The slurry obtained is dissolved in the minimum of water at 50-60 oC and
rapidly filtered. The salt crystallizes as light green needles. Allow the solid to dry under
vacuo. Determine the percentage yield, and transfer to a labeled vial.
E. Preparation of Potassium Hexa(thiocyanato)chromate(III)

Make an aqueous solution of potassium thiocyanate, KSCN (2.5 g), chrome alum,
KCr(SO4)2·12H2O (3.0 g) using distilled water (10 mL). Pour the solution into an
evaporating dish and place on a steam bath. Evaporate to dryness, to obtain a mass of red
crystals. Extract the solid, via suction filtration, using alcohol. The desired
K3[Cr(NCS)6], should dissolve very readily while K2SO4 remains as a residue. After
evaporation of the filtered alcohol extract, collect the dark red-violet crystals. Allow the
solid to dry under vacuo. Determine the percentage yield, and transfer to a labeled vial.

F. Spectroscopy of the Cr(III) Complexes.

Prepare aqueous solutions of tris(ethylenediamine)chromium(III) chloride, hexakis(urea)

chromium(III) chloride, potassium tris(oxalato)chromate(III), ion), potassium
hexa(thiocyanato)chromate(III), and Cr(NO3)3·9H2O (hexaaquochromium(III) nitrate)
and a toluene solution of tris(2,4-pentanedionate)chromium(III). The concentration of all
solutions should be such that the low energy absorbance maxima is between 0.2 and 1.5
absorbance units.

Obtain the absorbance spectrum for each complex. Determine the longest wavelength
maximum in units of nanometers. Convert the wavelengths (which correspond to ∆o) into
wavenumbers (cm–1) using the following relationship:

∆o = [1/λ (nm)] (1 x 107) cm–1

Arrange the ligands in order of increasing ∆o. Compare this series with the
spectrochemical series. Tabulate your data.

References

1. This experiment is adapted from: Szafran, Z.; Pike, R.M.; Singh, M.M. “Microscale
Inorganic Chemistry: A Comprehensive Laboratory Experience”, 1991, John
Wiley & Sons, New York, NY, pg 248 and Bailer, J. C.; Jones, E. M. Inorg.
Synth., 1939, 1, 37.

2. Tanabe, Y.; Sugano, S. J. Phys. Soc. Jpn. 1954, 9, 753.