o

Determination of in Cr(III) Compounds (Adapted from Szafran, Exp. 29)

INTRODUCTION
The d orbitals of a metal ion in an octahedral ligand or crystal field (i.e., surrounded by an
g 2g
octahedral array of ligands) are split into a higher energy (e ) and lower energy (t ) set, as shown
in the following energy level diagram.
o
The energy difference between the upper and lower energy levels is designated as , the
octahedral crystal field splitting. In the older literature, this energy difference is also known as
10 Dq.
o
The degree of splitting of the d orbitals (the magnitude of ) in octahedral complexes
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
compounds of the same metal in a given oxidation state. The only major variable, in this case, is
the ligands bonded to the metal. From the study of the spectra of such complexes it is possible to
arrange the various ligands in a sequence according to their ability to cause d-orbital splitting.
This series is known as the spectrochemical series and is given below:
2 4 2 3 2
halides < OHG < C O G < H O < NCSG < py < NH < en < phen < NO G < CNG, CO
2
It should be emphasized that the spectrochemical series is only an empirical correlation and is
o
determined from experimental data. The magnitude of approximately double one moves from
halide to CNG in the spectrochemical series. The cyanide ion has the strongest ligand field of all
common ligands.
The interpretation of the electronic spectrum of a d coordination compound is
1
straightforward. The spectrum shows only one dd band, corresponding to a transition from the
2g g
t level to the e level. In complexes with electronic configurations d where 1 < n < 9, the
n
spectral interpretation becomes more difficult, because of additional interactions between the d
electrons. More than one absorption band occurs in such systems.
In the case of Cr (d ) compounds, the spectral characteristics are reasonably easy to
3+ 3
interpret. It can be seen from the Tanabe-Sugano energy level diagram that the lowest energy
2
state (the ground state) is labeled A (pronounced quartet-A-two), corresponding to an electronic
4
2g
configuration of three electrons in the t level. There are several excited states as well. Keeping
in mind the visible selection rules, the major bands
seen in the visible spectrum will correspond to
transitions to other quartet states. These states in
2
order of ascending energy, are labeled T (two
4
2g g 1
electrons in the t , one in the e ), T , and another
4
1 2g g
T (one electron in the t , two in the e ). The
4
energy separation between the two lowest energy
2 2 o
levels, A and T , is . This band will be the one
4 4
with the longest wavelength in the spectrum. Thus,
although Cr(III) complexes show more complicated
spectra than that shown by d systems, the value of
1
o
may be directly calculated from the longest
wavelength band.
There are three main objectives for this experiment:
1. The investigation of the electronic spectra of
several common Cr(III) complexes:
2 6 3 3 2
[Cr(H O) ](NO ) A3H O (commercially
2 4 2 2
available), [Cr(H O) Cl ]ClA2H O (commercially
3 4
available), [Cr(en) ]SO (may be prepared here),
3 3
K [Cr(ox) ] (prepared previously), and
3
[Cr(acac) ] (prepared previously).
o
2. The determination of for each compound and arranging the ligands in order of crystal field
strength for comparison to the spectrochemical series.
2 4 2 2
3. The interpretation of the changes in a series of spectra of [Cr(H O) Cl ]ClA2H O obtained
over an extended period of time.
EXPERIMENTAL SECTION
Preparation of Complexes
3 3 2
Chromium(III) nitrate nonahydrate Cr(NO ) @9H O. In aqueous solution, it forms
2 6 3 3 2
[Cr(H O) ](NO ) A3H O. This is a commercially available compound. It can be used without
further purification.
3 2
Chromium(III) chloride hexahydrate, CrCl A6H O. This compound is also commercially
2 4 2 2
available. In aqueous solution, it initially forms [Cr(H O) Cl ]ClA2H O. It can also be used
without further purification.
3
Tris(2,4-pentanedionato)chromium(III), [Cr(acac) ]. This compound was prepared
previously.
3 3 2
Potassium tris(oxalato)chromium(III) trihydrate, K [Cr(ox) ]A3H O. This compound will be
prepared via the procedure below or product prepared previously will be used.
Safety Recommendations
Chromium(III) chloride hexahydrate (CAS No. 10060-12-5): Chromium compounds are
3 2 iv
considered mildly toxic. The reagent CrCl A6H O has MLD in mice of 801 mg/kg. Certain of
them have been listed as carcinogens by the EPA.
Chromium(III) nitrate nonahydrate (CAS No. 7789-02-8): Chromium compounds are
considered mildly toxic. ORL-RAT LD50: 3250 mg/kg. The compound is harmful if inhaled or
swallowed.
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 has an irritating ammonia odor
(vapor pressure is 10 mm at 20EC), so it should only be used in the HOOD.
CHEMICAL DATA
Compound
FW Amount mmol bp (EC) mp (EC) Density
3 2
CrCl A6H O
266.5 266 mg 1.0 83 1.760
Ethylenediamine 60.10 1 mL 15.0 118 8.5 0.899
EXPERIMENTAL PROCEDURE
Part 1: Preparation of potassium tris(oxalato)chromium(III) trihydrate
In a 30-mL beaker, with a stir bar, dissolve 3 g of oxalic acid dihydrate in 7 mL of warm
water. Add to this solution 1 g of potassium dichromate in very small portions. When vigorous
effervescence ceases, boil the solution on a hot plate (carefully!) and dissolve in it 1.2 g of
potassium oxalate monohydrate. Allow the mixture to cool to room temperature, then add to it
1.5 mL of 95% ethanol and continue cooling in ice. Collect the blue-green crystals on a Gooch
crucible filter and wash them first with two portions of 8 mL 50:50 ethanol-water, then with two
8 mL portions of 95% ethanol and air dry the product.
Part 2: Preparation of tris(ethylenediamine)chromium(III) sulfate
Place 1 g of anhydrous chromium(III) sulfate, previously ground to a fine powder and dried at
110EC for a day, and 2 mL of 99% ethylenediamine into a 25-mL round-bottom flask equipped
with an air condenser and heated to 100EC in a water bath or with a heating mantle. Within an
hour the sulfate begins to lose its green color and powdery character. If this does not occur, a
drop of water may be added to catalyze the reaction.
Once the reaction is proceeding, shake the flask regularly so that any unreacted sulfate
becomes exposed to the amine. A brown mass will be produced which is left on the steam bath
for at least twelve hours (e.g., overnight). Break up the resulting orange mass and grind it into a
powder. Collect the tris(ethylenediamine)chromium(III) sulfate by suction filtration using a
Gooch crucible and wash with ethanol and air dry.
Characterization of Chromium(III) Compounds
Prepare 10 mL of 0.05 M (0.01 M of acac and ox) solutions of each complex in the solvents
designated below. Water is used as the solvent for all the complexes except the insoluble
3
[Cr(acac) ] complex, for which toluene is used. Obtain the visible spectrum (350-760 nm) of
3 2
each of these solutions separately, saving CrCl A6H O for last. Plastic cuvettes can be used for
3
the aqueous solutions but glass cuvettes must be used for the [Cr(acac) ] because of the solvent.
Collect a spectrum of the chromium(III) chloride hexahydrate solution hourly for 24 h.
For each of the spectra obtained, determine the longest wavelength absorption maximum in
o
units of nanometers (nm). Convert the wavelengths (which correspond to ) into fre-quency
units of reciprocal centimeters (cm ) using the following relationship:
-1
o
Arrange the various ligands in order of increasing . Compare this series with the spectrochem-
ical series. Tabulate your data.
QUESTIONS
1. Does the order of ligands obtained in this experiment correspond to the established order in
the spectrochemical series? Explain any deviations.
3 2
2. Account for the changes in the highest wavelength maximum for CrCl A6H O with time.
What reaction is occurring in solution?
REFERENCES
1. Gillard, R. D.; Mitchell, P. R. Inorg. Syn. 1972, 13, 184.
2. Sawyer, D. T.; Heineman, W. R.; Beeke, J. M. Chemical Experiments for Instrumental
Methods, Wiley: New York, 1984, p. 163.
3. Skoog, D. A. Principles of Instrumental Analysis, 3 ed., Saunders: Philadelphia, 1985,
rd
Chapter 7.
4. Weissberger, A., Ed., Physical Methods of Organic Chemistry, Vol. II, in Techniques of
Organic Chemistry, Interscience: New York, 1946, Chapter 17.
5. Silverstein, R. M.; Bassler, C. C.; Morrill, T. C. Spectrometric Identification of Organic
Compounds, 4 ed., Wiley: New York, 1981, Chapter 6.
th
GENERAL REFERENCE
Lever, A. B. P., Inorganic Electronic Spectroscopy, Elsevier: Amsterdam, 1968.