EXPERIMENT II

STABILIZATION OF RARE OXIDATION STATE-TRIS(THIOUREA) COPPER(I) SULFATE

When an element can exist in more than one oxidation state in aqueous solution, each oxidation state will
have different thermodynamic stability. In this experiment, two examples of the stabilization of an unusual
oxidation state of copper will be studied. The stability of CuI, which is generally less stable in comparison to
CuII in aqueous solution, will be achieved by complex formation using thiourea ligand that can function both
as -bond donor and -bond acceptor. It is to form stable complexes due to the neutrality principal.
Thiourea can coordinate to the metal via the sulphur atom.

Experiment 2-1:

16 Cu2+(aq) + 8 (H2N)2CS(aq) + 16 H2O(l) 16Cu+(aq) + S8(s) + 16 NH4+(aq) + 8 CO2(g)

Cu+(aq) + 3(H2N)2CS(aq) [Cu{(H2N)2CS}3]+ (aq)

Preparation of Tris(thiourea) Copper (I) Sulphate

Prepare a solution of thiourea I (2.5 g in 15 ml of water) and a solution of copper (II) sulphate
pentahydrate II (2.5 g in 15 ml of water) at room temperature. Cool the solution II in an ice-bath. Gradually
and slowly add the solution II to solution I while stirring continuously. Allow the mixture to stand in the ice
bath until white crystals or oily drops can be observed. Prepare another solution of thiourea (1 g in 10 ml of water),
and add this solution to the cool reaction mixture while stirring vigorously. Allow the final mixture to stand
for a while before filter the white crystals using a Hirsch funnel.

Recrystallization
Prepare a solution of thiourea (0.15 g in 30 ml water) containing a few drops of 1M sulphuric acid,
and use this solution to dissolve the crude product while heating. During the recrystallization the
temperature should not exceed 800C (maximum of 75oC to dissolve the product). The obtained solution is
then filtered through a pleated filter. The filtrate may also be heated until any precipitated crystals have
dissolved (a little colloidal sulfur passes the filter, so the solution will not become completely clear). The
solution is cooled down afterward to room temperature by standing for 2-3 h. The crystals are collected by
filtration with suction, washed with 5 ml portion of cold water, followed by 5 ml portion of alcohol and
dried in air overnight.
Record the yield of the title compound in gram.
Calculate the theoretical yield in gram and the actual yield in percent.

Note that this is one of the general methods of preparing compounds containing a metal in a low
oxidation state. The ligand in this case thiourea also functions as reducing agent, and the product in this case
is obtained as the dehydrate.

Complementary Work and Questions:

1. Prepare a solution of thiourea (1 g in 1M HCl 10 ml). Add a little copper powder and warm gently. Repeat
the experiment without thiourea. Comment.
2. What is the reducing agent in the above preparation?

Experiment 2-2:

Determine the percentage of sulfate in the product from Experiment 2-1

Ba2+ + SO42- BaSO4

NH2CSNH2 + H2O 2NH3 + H2S + CO2

Note that the complex must be decomposed before determining the sulfate content, otherwise on
the addition of barium chloride a thiourea compound is also precipitated. The complex is readily destroyed
by making use of its sensitivity to hydroxyl ion attack. The product was recrystallized from acidified
solution. Thiourea is also hydrolyzed by alkali.

Weigh out accurately about 1.00 g of the solid complex into a 250 ml beaker, provided with a
stirring rod and clock-glass cover. 50 ml of 2M NaOH are added, and the mixture is heated until the
evolution of ammonia has ceased (~30 mins). The copper precipitates as the sulfide. Filter and wash with
cold water. Acidify the combined filtrate and washings with 2M HCl. Heat the solution to boiling. Add
warm 5% barium chloride solution (5 g BaCl2.H2O in 100 mL of water ca. 0.2M) drop wise using an
eyedropper 10-12 ml. Stir the solution constantly during the addition. Allow the precipitate to settle for a
minute or two, before test the supernatant liquid for complete precipitation by adding a few drops of
barium chloride solution. If a precipitate is formed, add slowly a further 3 mL of the reagent. Allow the
precipitate to settle as before and test again. Repeat the operation until an excess of barium chloride is
present. When an excess of the precipitating agent has been added, keep the covered solution hot, but not
boiling for an hour (steam bath, low temperature hot plate) in order to allow complete precipitation. The
precipitate should settle readily, and a clear supernatant liquid should be obtained. Test the latter with a
few drops of barium chloride solution for complete precipitation. If no precipitate is obtained the barium
sulfate is ready for filtration using sinter glass (no. 4). Dry the precipitate in the oven at 100-1100C.
Calculate the percentage of SO4 in the sample.

Determination of copper in the product from Experiment 2-1

Prepare standard 0.01M Na2H2 (EDTA) solution

Dry approximately 4.0 g of Na2H2(EDTA).2H2O [M=372.25 gmol-1, H4(EDTA) =
(HOOC)2CH2CH2(COOH)2] for 2 h at 800C and cool in a desiccator. Accurately weigh and dissolve in
deionized water using 1000 ml volumetric flask.

Prepare Buffer solution

Dissolve 17.5 g NH4Cl in 142 ml conc. NH4OH and dilute to 250 ml with distilled water.

Standardization of the EDTA solution with 0.01 M CaCO3

Pipette 25.0 ml of 0.01M CaCO3 into 250 ml Erlenmeyer flask. Add approximately 25 ml of
deionized water followed by 2.0 mL of pH 10 buffer solution and a small quantity of Erichrome
Black T indicator powder, swirl the solution to dissolve the powder (1 g Erichrome Black T in 100 g
NaCl). The solution should appear wine red. Titrate the solution with the 0.01M Na2H2(EDTA) solution
until the color changes from red to a pale blue (end point). Repeat this procedure at least twice. Calculate
the concentration of the Na2H2(EDTA) solution.
Analysis of the complex for copper
Cu2+(aq) + H2(EDTA)2-(aq) Cu(EDTA) 2-(aq) + 2 H+(aq)

Weight approximately 0.10 g of the complex into a 250 ml beaker with as little water as possible.
Slowly add 5 ml of conc. HNO3 to the powder and 20 ml of DI water. The mixture is heated until the
evolution of nitrogen oxides has ceased. Allow the beaker and its contents to cool to room temperature.
The sample solution is transferred to 250 ml Erlenmeyer flask, wash the sides of the flask with small
amount of water and adjust the volume to approx. 50 ml with water. Add conc. ammonia solution
dropwise to the solution, until the solution has turned blue color. Add a little murexide indicator (0.1-0.2 g)
and titrate the solution with the 0.01M Na2H2(EDTA) solution until the indicator changes from green to
violet. What mass of the compound contains one mole of copper?

Complementary Work and Questions:

1. From the available infrared spectrum of the product, identify as many group frequencies as you can.
2. Draw the structure of the product.

References
1. G. Pass and H. Sutcliffe, Practical Inorganic Chemistry, Chapman and Hall, London, 1974.
2. N.V. Sidgwick, The Chemical Elements and Their Compounds, Oxford University Press, Oxford,
1962.
3. K. Swaminathen and H.M.N.H. Trving, Inorg Nucl. Chem., 1964, 26, 1291.
4. J.V. Quagliano, et at., J. Amer. Chem. Soc., 1958, 80, 527.
5. A.J. Vogel, A text book of Quantitative Inorganic Analysis, 3rd edition, Longmans, London, 1961.
(or new editions).
6. B.A. El-Sayed and M.M. Sallam, Temperature and frequency dependent electrical transport in
thiourea and tris(thiourea) coupper (I) sulphate, J. Mater. Sci.: Mater. Electron., 1999, 10, 63-66.
Infrared Spectrum of Tris(thiourea) copper (I) sulphate