EXPERIMENT 5: THE PREPARATION OF TRIS(THIOUREA) COPPER(I) SULPHATE

INTRODUCTION

The thermodynamic stability of each oxidation state will be different when an element exists in
multiple oxidation states within the aqueous solution. Two examples of copper's unique oxidation
state stabilization will be investigated during the experiment. Stability of Cu(i), which is generally less
stable than Cu(ii) in aqueous solution, is achieved by forming complexes using a thiourea ligand that
functions as both an σ bond donor and a accept π bonds. Due to the neutrality principle, it must be
formed into stable complexes. Thiourea is able to coordinate with the metal by means of a sulphur
atom (Geoffrey Pass B.Sc., 1974).

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

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

In terms of disproportionation into Cu 0 and Cu2+, the conventional electrode potentials utilizing the
convention for the reactions demonstrate that Cu + ions in aqueous solution are unstable (Geoffrey
Pass B.Sc., 1974).

Cu²⁺ + e⁻ = Cu⁺

Cu(I) in compounds with soft donor ligands gives rise to a wide range of interesting chemical
equilibria and geometric configurations, including polynuclear species. Traditionally, Cu(I) is often
considered in the form of two-coordinate linear tetrahedra and four-coordinate tetrahedra.
Recently, however, a number of three-coordinate planar complexes have been isolated and their
crystal structures have been solved. Planar coordination number is expected with soft ligands,
uncoordinated anions, and ligands with groups that's cumbersome (I. F. Taylor, 1974).

Thiourea (also known as thiocarbamide) is an organosulfur compound with the chemical formula
SC(NH₂)₂. Its structure consists of H₂N−C(=S)−NH₂. Thiourea is a reagent for organic synthesis and is
used in a variety of fields. In particular, it is a precursor to thiourea dioxide, which is used in the
textile industry as a reducing agent[1].

Tris (thiourea) copper (I)sulphate crystallizes in the tetragonal system. The crystal Full three-
dimensional X-ray data were used to determine the structure. The structure is ionic, with sulphate
ions and infinite spiral chains of [Cu(thiourea)₃]⁺ of the usual tetrahedral configuration for
monovalent copper by sharing one of the three sulfur atoms of the thiourea ligands (SALLAM, 1999).

PROCEDURE
 (a) Synthesis of tris(thiourea) copper(I) sulphate

Thiourea solution was prepared by dissolving SC(NH₂)₂ (2.501g, 0.03286mol) in 15ml of deionized
water and copper(II) sulphate pentahydrate (2.505g, 0.1003mol) was dissolve in 15ml of deionized
water to prepare a solution. The two solutions were cooled and copper(II) sulphate pentahydrate
solution was slowly added in the thiourea solution. The mixed solutions were stirred continuously
until all the copper(II) sulphate solution was added. The solution was allowed to stand until white
crystals formed. A cold thiourea (1.009g, 0.6132mol) solution was prepared by being dissolved in
10ml of water and the solution was added to the mixture. The mixture was stirred vigorously,
allowed to stand for 5 minutes and then filtered. The product was recrystallized by dissolving it in
thiourea (0.1524g, 0.002002mol) solution prepared in 30ml of deionized water containing 5 drops of
1M sulphuric acid. The solution was heated up to 75°C to dissolve the product then cooled to form
crystals. The crystals formed were filtered, then washed with 5ml of cold water and 5ml of ethanol.

(b) Complementary work

Tris(thiourea) copper(I) sulphate (0.5001g, 0.0007355mol) was decomposed by dissolving it with

20ml of 50% nitric acid. The solution was evaporated to 2ml, ensuring that no part of the solution is
evaporated to dryness. The hot solution was cooled and, the sides of the flask and the bottom of the
watch glass was washed. The solution was diluted to 50ml and 2M ammonia aqueous was added
until there was a fainting blue precipitate. The Precipitate was filtered and dissolved in 2M acetic
acid and 50% of potassium iodine 10ml solution was added. The solution was then titrated with
standard sodium thiosulphate solution.

RESLTS AND DISCUSSION

(a) Synthesis of tris(thiourea) copper(I) sulphate

Table1: Mass of the product.

Mass of the filter paper + product (g) 4.3619

Mass of the filter paper (g) 0.8915
Mass of the product (g) 3.4704
Table 1: showing mass of the product.

Balanced equations are as follow:

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

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

Molar Masses:

(H₂N)₂CS= 76.12 g/mol

CuSO4·5H2O= 249.685 g/mol

Number of moles for reactants calculations

n = m/Mr

2.5011 g
n(thiourea)=
76.12 g /mol
 = 0.03286mol

2.5051 g
n(copper)=
249.685 g /mol
= 0.01003mol

Identifying the limiting reagent

mole ratio of the reaction for reactants is CuSO₄ : (H₂N)₂CS

0.01003 : 0.03286

16 8

= 0.0006270 : 0.004107

Therefore, copper(II) sulphate is the limiting reagent. From reaction 1, mole ratio of Cu²⁺ to Cu⁺ is
16:16 and the moles of copper(I) product is 0.01003mol.

From reaction 2, mole ratio of Cu⁺ to complex is 1:1.

Molar mass of the complex is:

Mr= 679.9g/mol

Because of the 1:1 ratio moles of the complex produced equals moles of Cu⁺ in the reaction.

n(complex)= 0.01003mol

m=n.Mr

m= (0.01003mol)(679.9g/mol)

m=6.821g

Yield:

Actual yield
Percentage yield=
Theoritical yield
3.4704 g
= ×100
6.821 g
=50.87%

Complementary work

The half-filled 3p orbitals of the sulphur atom bind to the metal to form a bond and the lone
pairs of the Sulphur atom make the π bond.

A solution containing 1 g of thiourea was prepared in 10 cm-3 of HCl and 1 g of copper

powder was added. The addition of the copper powder turned the solution brown and
then muddy when heated The experiment was repeated without thiourea and the
solution was blue.
 Ammonia

−3 m
2 M ×50 × 10 mol=
35 , 05 g/mol
¿ 3,505 g

m
V=
ρ

100 3,505
¿ ×
25 % 0.9 g /cm3

¿ 15.58 ml of ammonia ∈50 ml of water is 2 M

Acetic Acid

−3
2 M ×10 × 10 L× 60.052 g

¿ 1.201 g

m
V=
ρ

100 1.201 g
¿ ×
99 % 1.06 g /cm3

3 3
¿ 1.1445 cm of acetic acid∈10 cm of water is 2 M

There are 3 major absorptions that indicate the presence of the product. The band at 3394.79 cm -1
shows N-H stretch, the band at 1600.82 shows N-H bend. The band at 1364.86 cm -1 indicates sulfate
stretching. These bands are from the primary amine in thiourea and sulphate respectively. There is a
band at 3455.41 cm-1 from the O-H stretch indicating the presence of water molecules in our
structure, could be that our product did not completely dry.

CONCLUSION

1. BYJUS. (n.d.). Thiourea (CH4N2S) - Structure, Molecular Mass, Physical,chemical Properties,

Uses , Health hazard and FAQs of Thiourea. [online] Available at:
https://byjus.com/chemistry/thiourea/ [Accessed 13 Mar. 2024].