SYNTHESIS OF TERTAAMINE COPPER (II)

Monday, April 9th 2018

1. INTRODUCTION
1.1 Objectives
Studied the reaction of preparation complex salt of Tetraamine copper (II) sulfate hydrate
[Cu (NH3) 4] SO4.xH2O.
1.2 Literature Review
Salt is a compound that is generally the result of acid and base reactions that can be
acidic, alkaline, or neutral. Salt solution can conduct electricity. Strong salts will exhibit
higher electrical conductivity than weak salts (Arsyad, 2001).
There are two possible salts to be formed when two or more simple salts mixed, ie a).
Salt whose lost identity when in solution (water solvent). This salt is called double salt, and
b). Salt whose has same identity when in solution (water solvent). This salt is called complex
salt (Rosbiono, 2012).
Complex is a compound formed of metal ions that bind to the ligand in a coordinated
covalent manner. The coordination bond is a covalent bond in which the ligand provides a
pair of electrons to the metal ion for bonding. The bonds occur when the metal ions become
central atoms, providing empty orbitals for the ligand pairs of electrons to coordinate
(Elmila&Martak, 2010).
CuSO4.5H2O crystals are one of the most needed materials in the industry. Utilization
of CuSO4.5H2O is very wide. CuSO4.5H2O crystals of this blue crystalline solid can be
prepared by reacting copper with sulfuric acid and nitric acid which is then heated and until
crystals are formed. In addition to copper metal raw materials, CuSO4.5H2O crystals can also
be made from used copper or copper in sponge form obtained from CuCl2 solution (Fitrony,
et al, 2013).
Cu(I) nor Cu(II) are stable ionic species in neutral and alkaline solutions without
complexing agents, NH3 or CN-. In the presence of excess ammonia, however, Cu(I) and
Cu(II) are stable as Cu(NH3)2+ and Cu(NH3)42+ in neutral and alkaline solutions, respectively.
The oxidation-reduction reactions of Cu(II)/Cu(I) and Cu(I)/Cu. The oxidation-reduction
potential of Cu(NH3)42+/Cu(NH3)2+is greater than that of Cu(NH3)2+/Cu, which indicates that
 Cu(NH3)2+can work as an oxidizing agent for metallic copper in an ammoniacal alkaline
solution. Also, the oxidation-reduction potential of Cu(I)/Cu is greater than that of hydrogen
evolution, which indicates that Cu(I) can be preferentially reduced to metallic copper
(Koyama, et all, 2006).
The reaction between Cu2+ and OH-ions at various concentrations depends on the
method. The addition of hydroxide ions to the copper (II) sulfate (0.1 - 0.5) solution, at a rate
of 1 mL/minutes, results in the precipitation of blue bronze gelatin (II) hydroxysulfate,
[CuSO4nCu(OH)]2 instead of Cu(OH)2 according to the reaction equation:

(n + 1) [Cu (H2O)6]2+ (aq) + SO4 (aq) + 2n OH- (aq) → [CuSO4] nCu(OH)12 (s) + 6(n + 1) H2O (l)

The precipitation reaction occurs perfectly at pH = 8 and the n values varying

according to the reaction temperature and the rate of addition of the reactant, for example at a
rate of addition of the reaction of 1 ml / min, the reaction yields CuSO4 3Cu (OH)2 if the
reaction takes place at 20°C and CuSO4 4Cu (OH)2 at 24°C (Sugiyarto 2003).

2. EXPERIMENTAL METHODS
2.1 Apparatus and Reagent
2.1.1 Apparatus
Apparatus that we need are beaker glass 50 mL, funnel, measurement glass 50 mL,
watch glass, stirring bar, dropping pipette, spray bottle, filter paper, aluminum foil,
analytical balance, electrical heater, and melting point apparatus.

2.1.2 Reagent
Reagents that we need are CuSO4.5H2O crystal, (NH4)2SO4 solution, KSCN 0.5 M
solution, concentrated ammonia, etanol solution, and aquades.
 2.2 Procedures
Making Complex Salt
Copper (ii) sulphate pentahydrate weighed as much as 1.25 grams. Then copper (ii)
sulphate pentahydrate are dissolved with 5 mL Aquades in a 50 mL beaker glass.
Concentrated ammonia is added dropwise in solution until re-formed precipitate soluble
(excess ammonia). After that the solution is allowed to stand at room temperature. 20 mL of
ethanol is added with a dropper drops slowly through the glass wall until it forms two layers
(bottom = blue glass, top = clear). The solution was sealed with aluminum foil and silenced,
changes were observed until crystal was formed. The filter in the filter was placed in a watch
glass then the crystal was dried in ±60°C oven for 2 hours then the crystal was weighed.

Calibration
Mass of complex salt is weighed and dissolved in 10 mL of aquades. Absorbance
spectrum is based on 300-800 nm. 2 mL of the structure was reacted with 1mL KSCN
0.5Mp, and the absorbance spectrum was performed at 300-800 nm. Then the solution of
NaCl, CuSO4, and FeCl3 was made with a concentration of 0.025M. Measure the
conductivity of each solution. The obtained complex salt samples were placed on the ATR-
FTIR sample holder and measured the IR spectra from the sample. The results obtained are
compared with their constituent compounds.

3. RESULT AND DISCUSSION

3.1 Result
Procedures Observation
A. Dissolve copper (II) sulfate pentahydrate Mass = 1.2540 grams
V.Aquades = 5 mL
Dissolution is done inside = Beaker glass 100
mL
Color of solution =Deep sky blue
Form of CuSO4.5H2O = Powder
B. Adding concentrated ammonia V. Ammonia = 49 drops

C. Adding ethanol through glass wall
D. Close beaker glass with aluminum foil
E. Filter out solution and dry precipitate
Color of solution = Blue
V. Ethanol = 20 mL
Top layer color = Colorless
Bottom layer color = Navy precipitate
Volume of solution = ± 35 mL
Time = 4 days
Mass = 0.3437 grams
Volume of solution = ± 25 mL
Temperature = 60°C
Color of precipitate = Blue

3.2 Discussion
Experiment of making a complex salt is done by reacting CuSO4.5H2O with a
concentrated ammonia solution so the color of the solution becomes blue. Ammonia solution
(NH3) acts as a provider of ligands, and CuSO4.5H2O crystals serve as a central atomic provider,
while aquades are as Cu2+ complexes which then replace H2O ligands with NH3, NH3 is a strong
ligand that can push neutral H2O ligand so that the color change from deep sky blue into blue. In
this process ethanol is added slowly through tube wall, the purpose is ethanol don’t mix with the
solution but to cover the solution. If ethanol mixed, ethanol can react with central atom Cu2+ to
form Cu (OH)2. In addition, ethanol serves to prevent evaporation of ammonia, because if the
ammonia evaporates, the ligand will run out. Then precipitate is allowed to form crystals.

3.2.1 Conductivity Test

Resulting precipitate is dissolved in Aquades, but when dissolved all precipitate don’t
dissolve so H2SO4 is added. This is because H2SO4 solution has a high solubility so that
sample is easier to ionize.
To test the conductivity of the sample, then we must calculate the concentration of the
sample. Based on the calculation, obtained M sample 0.0098 M. Because sample solution has
different molarity with conductivity comparative solution, then the comparative solution
diluted so that concentration is equal to the sample solution. The result of conductivity test
with T = 27.9°C:
 Water = 2.00μS, has 3 ions;
CuSO4 = 609μS, has 2 ions;
NaCl = 637μS, has 2 ions;
FeCl3 = 2.01mS, has 4 ions;
Sample = 931μS;
Conductivity is ability of a solution to conduct electricity. Conductivity is used for the
size of the electrolyte solution. Electrolyte concentration greatly determines the amount of
conductivity. The conductivity of a solution depends on:
a. Number of ions present
b. Velocity of ions at potential difference between two electrodes.
Based on the experiment, result of conductivity of sample is similar to NaCl and
CuSO4. This is because the amount of sample ions and NaCl and CuSO4 solutions are same.
NaCl is an ionic compound which when dissolved in aquades will be fully ionized and
transformed into ions in solution of Na+ and Cl- ions, as well as CuSO4 solutions and sample
solutions which may turn into ions in solution. Number of ions held by sample solution is 2.

3.2.2 Test using UV-Vis

For test using UV-Vis, sample is divided into 2 parts. First, sample without KSCN
solution and second with KSCN solution. Maximum sample wave without KSCN was 618
nm with absorbance 1.680 and maximum wave sample with KSCN was 619 nm with
absorbance 1.152. While for maximum wave of CuSO4 was 817 nm with absorbance 3.188.
Based on these data means addition of KSCN solution doesn’t affect the complex salt
solution because different maximum wave not much. The addition of KSCN solution doesn’t
make NH3 as a ligand is replaced by SCN. Based on spectroscopic test result, NH3 ligand is
stronger than SCN.

3.2.3 Test using FITR

Test with FTIR using a transmission method in which the sample should be made
palette. Powder sample was added with KBr powder to form a palette. Reason using is KBr
didn’t affect the sample. Sample comparison with KBr is 1:10
 41
40

35

30 897.55cm-1

25
507.61cm-1
%T

20 675.62cm-1

15
1621.99cm-1
3232.14cm-1 1403.46cm-1
10
3318.63cm-1 1264.75cm-1
3439.00cm-1 1120.80cm-1 618.64cm-1
5
2
4000 3500 3000 2500 2000 1500 1000 500 370
cm-1

Based on FTIR data obtained and referring to the research of Nurvikaet al (2013),
wave 3318.63 cm-1 shows the existence of N-H bond. In the 507.61 cm-1 wave indicates a
Cu-N bond. In wave 3232.14 cm-1 and 3439.00 cm-1 shows the existence of O-H bond. In
wave 1403.46 cm-1 indicates the presence of Cu-S bond. In wave 1621.99 cm-1 shows the
existence of S-O bond. In wave 1264.75 cm-1 shows the existence of C-N bond.
4. CLOSING
4.1 Conclusion
1. The yield obtained from the experiment was 30.125%.
2. From conductivity test results, the number of ions [Cu(NH3)4]SO4 is 2.
3. The addition of KSCN solution doesn’t affect the complex salts.
4.2 Suggestion
1. Be careful when dripping with concentrated ammonia.
2. Be careful when closing beaker glass with aluminum foil, because if beaker glass was
shaking then there is the possibility of ethanol mixed with complex salts.
3. When complex salt solution dripping into cuvette, ensure that no fingerprints were stuck
in the cuvette.
5. REFERENCES
Arsyad, M. Natsir. 2001. Kamus Kimia Artidan Penjelasan Istilah.Gramedia: Jakarta.
Elmila, Izza and Fahimah Martak. 2011. “Peningkatan Sifat Magnetik Kompleks Polimer Oksalat
[N(C4H9)4][MnCr(C2O4)3] dengan Menggunakan Kation Organik Tetrabutil
Amonium”. Jurnal Prosiding Skripsi Kimia FMIPAUNESA.
Fitrony, Rizqy F., Lailatul Q., and Mahfud. 2013. “Pembuatan Kristal Tembaga Sulfat Pentahidrat
(CuSO4.5H2O) dariTembaga Bekas Kumparan”. Jurnal Teknik Pomits, Vol. 2, No.1.
Koyama, K., Mikiya T., and Jae-chun Lee. 2006. “Copper Leaching Behavior from Waste Printed
Circuit Board in Ammoniacal Alkaline Solution”. Materials Transactions, Vol. 47, No.7.
Nurvika, Dian.,Suhartana, and Pardoyo. 2013. “Sintesisdan Karakter Senyawa Kompleks Cu(II)-
EDTA dan Cu(II)-C6H8N2O2S2”. Jurnal Penelitian,Vol. 1, No. 1.
Rosbiono, Momo. 2012. Terminologi – Karakteristik – Metode Pendeteksian – Aplikasi,
Klasifikasi, Tatanama dan Isomerisasi Senyawa Koordinasi. Surabaya:UNESA.
Sugiarto, Kristian. 2003. Kimia AnorganikII. Malang: FMIPA UPI.

6. APPENDIX
Calculation of dilution
𝐺𝑟𝑎𝑚𝑠 1000
Msample = ×
𝑀𝑅 𝑉𝑜𝑙𝑢𝑚𝑒
0.1556 1000
= ×
317.5 50
= 0.0098 M
V1 × M1 = V2 × M2
V1 × 0.25 = 50 × 0.0098
V1 = 1.96 mL

Calculation% Yield Obtained

Based on experiment, we got some data for calculation % Yield ofTetraamine Copper (II).
 Initial mass of CuSO4.5H2O = 1.2540 grams
 Result mass of Tetraamine copper (II) sulfate = 0.3437 grams
1.2540 grams
 Mole CuSO4.5H2O = =5.026 × 10-3 moles
249.5 grams/mole
 Mole NH3
ρ = 0.899 g/mole
If we assumed 20 drops = 1 ml, then 49 drops = 2.45 ml
Mass NH3 = 0.899 g/ml × 2.45 ml
= 2.2025 grams
2.2025 grams
Mole NH3 = = 0.1293 moles
17.031 grams/mole

 Reaction
[Cu(H2O)5]SO4 + 4NH3 → [Cu(NH3)4]SO4 + 5 H2 O
Initial 0.0050 mole 0.1293 moles
Reaction 0.0050 mole 0.0050 moles 0.0050 moles 0.0050 moles
Residue - 0.1243 moles 0.0050 moles 0.0050 moles
 Mass of [Cu(NH3)4]SO4
Mass = 0.0050 moles × 227.5 gram/mole
= 1.1375 grams
 % Yield
𝑟𝑒𝑠𝑢𝑙𝑡𝑠 𝑤𝑒𝑖𝑔ℎ𝑡
%= × 100 %
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑤𝑒𝑖𝑔ℎ𝑡
0.3437 𝑔𝑟𝑎𝑚𝑠
= × 100 %
1.1375 𝑔𝑟𝑎𝑚𝑠

= 30.215 %
Picture when experiment

Crystal of Mixture of complex

CuSO4 soluiton
CuSO4.5H2O salt and ethanol

Separating complex salt [Cu (NH3) 4] SO4.xH2O

Conductivity test Cuvette for UV-Vis Palette for FTIR test

test