Experiment 7

DETERMINATION OF MAGNETIC SUSCEPTIBILITY OF

COORDINATION COMPLEXES

Introduction:

Transition metals, by definition, have at least one oxidation state with an incomplete d or f subshell.
Since electron spin and orbital motion can generate a magnetic field, the magnetic properties of
transition metals are of great importance in determining the oxidation state, electronic
configuration, and so on.

During complex formation, transition metals can either have all their valence electrons paired up
(low spin) termed diamagnetic or have one or more unpaired electrons (high spin) called
paramagnetic. Diamagnetic complexes show very small magnetic moments compared to
paramagnetic complexes. The number of unpaired electrons on a given metal ion determines the
magnetic moment and is measured in Bohr magnetons (BM).

Magnetic moments are not measured directly. Instead, the magnetic moment is calculated from the
magnetic susceptibility which by definition is “The ratio of the intensity of magnetism induced in
a substance to the magnetising force or intensity of field to which it is subjected”.

In this experiment the magnetic susceptibility of two complexes will be determined using the
Evan’s method (named after a professor at Imperial College who collaborated in the designing of
the balance). The balance works on the basis of a stationary sample and a moving magnet. When
the sample is introduced between two magnets, a deflection is recorded if the sample exerts any
force due to unpaired electrons.

Apparatus for measuring the magnetic behaviour of a Sample:

The substance is weighed on a very sensitive balance in the absence of an external magnetic field.
See the figures on page 34. Figure A, if a substance is diamagnetic (contains no unpaired
electrons), its apparent mass is unaffected (or slightly reduced) when the magnetic field is “on”.
Figure B, if a substance is paramagnetic (contains unpaired electrons), its apparent mass increases
because the balance arm feels an additional force when the field is “on”. This method is used to
estimate the number of unpaired electrons in transition metal compounds.

Packing of sample tubes:

Grind the prepared complex to obtain a reasonably fine and uniform powder. A small amount of
sample (complex) is then introduced into the weighed sample tube, and the bottom of the tube
gently tapped a number of times to shake the solid down. Care should be taken when packing since
the major error arises from inhomogeneous packing. This procedure is repeated until about 2.5 –
3.5 cm length of the sample is obtained. Note that the top of the sample is horizontal.
Operation of the Evan’s Balance:

1. Turn the range knob to the x1 scale and allow 10 minutes warm-up period before use. If the
balance is to be used frequently it should preferably be left on continuously.

2. Adjust the zero knob until the display reads 000. The zero should be adjusted on each scale
used.

3. Weigh an empty sample tube on an analytical balance and record its mass. Place the empty
tube into the tube guide and take the reading, Ro.

4. Pack the sample as suggested in the procedure above and record the mass of the sample in
grams and the sample length, l, in cm.

5. Place the packed sample tube into the tube guide and take the reading, R.

6. If the display goes off scale, turn the RANGE knob to the x10 scale and re-zero and multiply
the reading by 10.
The mass susceptibility, Xg, is calculated using the following formula:

C Bal ( R  Ro )l
Xg 
109 m
Where, l = sample length (cm)
m = sample mass (g)
R = reading for tube + sample
Ro = empty tube reading and
CBal = balance calibration constant

Calculation of Magnetic moment:

Once the mass susceptibility is obtained, convert this to molar susceptibility, Xm, by multiplying
by the molar mass. Then calculate the magnetic moment, using the following formula:
 = 2.84 XmT

where  is magnetic moment and T is the room temperature in K. After calculating , cross-
check with the expected values (from the Appendix I ) to determine the number of unpaired
electrons present in the complex.

1. Preparation of Copper(II) Acetate Monohydrate:

Experimental:

Safety Recommendation:
Copper(II) sulphate pentahydrate: This compound is not dangerous but usual precautions
should be taken.
Sodium hydroxide: This is harmful if swallowed, inhaled, or absorbed through the skin. It
is extremely caustic, especially on wet surfaces.
Acetic acid: Harmful if swallowed, inhaled, or absorbed through the skin. Concentrated
acetic acid is corrosive. It has been found to have effects on male fertility and to have
behavioural effects on new borns.

In a 100 cm3 beaker equipped with a magnetic stirring bar, dissolve 2.5 g of Cu(II) sulphate in 5
cm3 of water. Stir the mixture, and warm it to 40-50 0C on a sand bath to aid the dissolution.
Using a Pasteur pipette, add conc. NH3 to the warm, stirred, light blue solution, until the intense
blue colour of the complex is evident. During the addition if a precipitate of copper hydroxide
appears, it redissolves with further addition of NH3.

Add 0.8g of sodium hydroxide flakes to the deep blue solution, and stir the mixture for 15–20
minutes at 55–66 0C. A light blue solid of copper (II) hydroxide precipitates during this time.
Allow the mixture to cool to room temperature and collect the precipitate by vacuum filtration.
Wash the blue solid with three 10 cm3 portions of warm water.
Transfer the solid Cu(OH)2 to a 100 cm3 beaker, and dissolve it in a minimum amount of 10%
acetic acid by using a droper. Warming on the sand bath with stirring aids the dissolution process.
Concentrate the solution nearly to dryness (in fume hood) by warming it on the sand bath. Dry the
product on a filter paper.

1. Calculate the percentage yield.

2. Determine the magnetic moment using the Evan’s balance.

Questions:

1. Draw the structure of the complex prepared.

2. Will it be a high or low spin complex?
3. Calculate the number of unpaired electrons in the complex.

2. Preparation of tris(2,4–pentanedionato) chromium(III):

Experimental:
Safety Recommendation:

Chromium(III)chloride hexahydrate: Chromium compounds are considered mildly toxic.

Some of them however, have been listed as carcinogens.
2,4–Pentanedione (Acetylacetone; acacH). This compound is a mild irritant to the skin and
the mucous membranes. Also it is Flammable.
Urea: Not dangerous. Classified as a diuretic and normal precautions should be taken.

In a 10 cm3 Erlenmeyer Flask fitted with a microwatch glass cover and containing a magnetic
stirring bar, place 2 cm3 of distilled water and 130.0 mg of Chromium(III)chloride hexahydrate.
When the chromium complex has dissolved, add 500.0 mg of urea and 400 L of acetylacetone.
A large excess of acacH is used, as it helps the reaction go to completion.

Clamp the Erlenmeyer flask in a 150 cm3 beaker of boiling water set on a magnetic stirring hot
plate. Heat the mixture, with constant stirring, for about 1h. As the urea releases ammonia and the
solution becomes basic, deep maroon crystals will begin to form. These form as a crust at the
surface of the reaction mixture.

Cool the reaction flask to room temperature. Collect the crystalline product by suction filtration
using a Hirsch funnel. Wash the crystals with three 200 L portions of distilled water. Dry the
product on a clay tile or on a filter paper.

Questions:

1. Calculate the percentage yield and the magnetic moment.

2. Draw the structure of the complex prepared.