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Experiment 5

Identification of Cobalt(III) Complexes: Conductance Measurement


Technique
Objectives
1. To synthesize Cobalt(III) complexes
2. To study how to identify the complexes using the Conductance
Technique

Measurement

Theory
There may be occasions when you need to confirm that a compound is ionic and/or
determine the number of constituent ions without resorting to a crystal structure determination.
Such a situation might arise, for example, when it is unclear whether an anion is bonded to the
metal or simply present in the compound as a counterion, and this can often be resolved by
conductivity measurements. The conductance of a solution is a measure of the ability of that
solution to carry a current. The transfer of electricity through the solution results from the
movement of ions. Conductivity of a solution varies with the number of ions in solution, i.e. with
concentration. In order to compare conductivities of different compounds some account must
be taken of concentration.
In the resistance (R) of an electrolyte is measured using an AC Bridge circuit, and is
related to the resistivity (defined as the resistance of the solution in a cell with
1 cm x 1 cm electrodes that are 1 cm apart) by the cell constant C
R = C
If C is not known, it must first be determined by measuring the resistance of a standard
electrolyte such as 0.02 M potassium chloride solution, which has a conductance of 2.768 x 10-3
S (the unit for conductance is the siemen S; 1 S = 1 -1). The cell constant can then be
calculated by using the expression:
C = 0.002768 R

Hence the conductance of any solution in the cell can be determined, but this must be
standardized to enable comparison with other substances and is therefore converted to molar
conductivity , defined as the conductance of a 1 cm3 cube of solution containing one mole (or
formula weight) of solute. If the molar concentration of the electrolyte is c then:
=

= molar conductivity; S cm2 mol -1


= electrical conductivity; S cm-1
C = concentration in mol cm-3 (caution !!!)
For example, consider equimolar solutions of sodium chloride and barium chloride. The
concentration of chloride ions in the solution of barium chloride is double the concentration of
chloride ions in the solution of sodium chloride. The amount of charge carried by one barium ion
is double the amount of charge carried by sodium ion. Molar conductivity will therefore change
with the number of ions produced per mole of solute.
Thus, the number of ions in ionic salts relate to molar conductivity , as shown below :
Molar conductivity The number of ions
(S cm2mol-1)
NaCl
CaCl2
LaCl3
[Pt(NH3)6]Cl4

123.7
260.8
393.5
522.9

2
3
4
5

118-131
235-273
408-435
~560

The solutions are thermostatted at 25C as varies with temperature in aqueous solution.
Non-aqueous solvents of choice are nitromethane and acetonitrile but their toxicity must be
taken into account when using them.
A study of molar conductivity will provide information as to the number of ions produced
per mole of a given solute. Conductance measurements on a variety of solutions show that the
molar conductivity increase with decreasing concentration, and approaches a constant value in
very dilute solution. When determining molar conductivities it is advisable to use very dilute
solutions. For very precise work measurements should be made at several concentrations and
the values obtained extrapolated to infinite dilution.

Conductance measurements are of assistance in determining solubility of relatively


insoluble salts, measuring salt hydrolysis, titrimetry, and determining the structure of transition
metal complexes.

Procedures
5.1 Preparation of [Co(NH3)4CO3]NO3
In a 250 ml beaker, dissolve about 5 g of (NH4)2CO3 in 15 ml water, and then slowly add
15 ml of concentrate aqueous ammonia (specific gravity 0.88 g cm -1). Add a solution of 3.5 g
Co(NO3)2 in 7 ml water with continuous stirring. Now slowly add 3 ml of 30% H 2O2.
Caution: Hydrogen peroxide can cause burns, and skin contact must be avoided.
Wear rubber gloves.
Cautiously heat the solution until the volume is reduced to nearly 25 -30 ml (use HOOD).
Take care not to boil the solution. During evaporation, slowly add 1.25 g (NH4)2CO3. Filter the
solution whilst still hot with suction (solid precipitate on filter paper discard at waste container
No. 8 but a filter paper discard at waste container No. 7). Keep the filtrate (dark purple) solution
in beaker and then allow the red precipitate of [Co(NH3)4CO3]NO3 to settle in ice water bath.
Filter with suction and wash the precipitate product with cold water (filtrate discard at waste
container No. 4) and finally in 95% ethanol (filtrate discard at waste container No. 2).

5.2 Preparation of Co(NH3)5Cl3


Dissolve 1 g of [Co(NH3)4CO3]NO3 (from section 5.1) in 10 ml water and add about 2 ml
of concentrated hydrochloric acid. The disappearance of CO2 gas indicates the enough adding
of HCl. Neutralize the solution with concentrated aqueous ammonia, and keep it excess for 1 ml.
Heat the solution for about 10 minutes, take care not to boil it. Leave it to cool for a while. Then,
add 15 ml of concentrated HCl, and heat again for about 15 minutes. A purple crystalline
precipitate was formed after allow it to cool to room temperature. If this does not appear, leave it
to stand for 5 minutes in a beaker of ice. Wash the precipitate with 10 ml of cold water by
decantation. Repeat the washing two to three times (washing solution discard at waste

container No. 4). Now, filter by suction and wash the precipitate with 95% ethanol (washed
solvent discard at waste container No. 2). Allow the precipitate to dry in an oven at 120C.
Record the yield.

5.3 Measurement of the Conductivity of Co(NH3)5Cl3 Complex


The conductometer apparatus should be already set up in the laboratory. Measure the
electrical conductivity () of freshly prepared 0.001 M Co(NH3)5Cl3 complex in 100.00 ml
volumetric flask. Calculate the molar conductivity (), and relate to the number of ions, in order
to conclude the formula of this octahedral complex. Solutions of products discard at waste
container No. 4. Solid product discards at waste container No. 8.

Prelaboratory Problems
1. Suggest the method to analyze percent of ionic chloride in [Co(NH3)5Cl]Cl2 complex.
(Hint: ionic Chloride is more reactive than chloro ligand in the coordination sphere)
2. Suggest the method to analyze percent of cobalt(III) in [Co(NH3)4CO3]NO3 complex.

Postlaboratory Problems
1. What do you think if you leave [Co(NH3)5Cl]Cl2 complex solution stand overnight before
measuring the conductivity, increase or decrease? Why?
2. Comment on the results and on the structure of Co(NH3)5Cl3 octahedral complex.

References
1. Angelici, R.J., Synthesis and Technique in Inorganic Chemistry 2nd ed., W.B. Saunders
Company, Philadephia,1997.
2. Pass, G. and Sutcliffe, H. Practical Inorganic Chemistry: Preparations. Reactions and
Instrumental Methods, Chapman and Hall, London,1974.