March 31st 2015

EXPERIMENT V
SYNTHESIS OF TETRAAMINCOPPER(II)SULPHATE
A. Objectives
1. Study the synthesis of complex salt tetra amin copper (II) sulphate as a result of
the reaction between ammonia and cupri sulphate.
2. Study the properties of complex salt tetra amin copper (II) sulphate.
B. Theoretical Basis
Theory coordination of Warner is the basis for coordination chemistry. This
theory basing their secondary valence may explain the properties and stereochemistry
of many complex compounds. However, with the development of the theory of atom
deep perverse modern and the fact that Warner's theory can not explain many
properties of complex compounds, arise new theories of coordination chemistry.
Bond theory in complex compounds originally given by Lewis and Sidgwik. This
theory because it can not explain the geometric forms of the compounds was later
abandoned. Three theories that then arises is:
a. Valence Band Theory (VBT)
b. Crystal Field Theory (CFT) and
c. Molecular Orbital Theory (MOT)
(Sukardjo, 1985)
Transition metals can form complex ions are diverse. An example is copper.
Copper is a metal pink, soft, malleable, and clay. Copper melts at 10380C. Due to the
positive standard electrode potential (+0.34 V for couples Cu / Cu 2+), copper is not
soluble in hydrochloric acid and dilute sulfuric acid, although the presence of oxygen
can dissolve a little copper. Salts of copper (II) anhydrous, such as Copper (II) Sulfate
Anhydrous CuSO4, white (or slightly yellow). In aqueous solutions always contained
tetraakuo complex ion (G. Svehla, 1990).
Copper (Cu) is one of the lightest metal and the least active. Cu+ experience
disproporsionisasi spontaneously at standard state (default). This does not mean the
compound solution of Cu(l) not be formed. To assess the state of how the Cu (l) and
Cu (lI) is formed, which is made (Cu+) enough in many water solution, Cu 2+ will be
in large quantities (because its concentration should be about two million multiplied
by the square of the Cu2+). Disproporsionisasi this would be perfect. On the other
hand if the Cu+ kept very low (as in the slightly soluble substances or complex ions
steady). Cu2+ is very small and copper (I) to settle.
The addition of aqua ligands in solution causes the formation of complexes
with the exchange of water molecules sequentially with NH3. For example, species
[Cu(NH3)(H2O)5]2+ [Cu(NH3)4(H2O)2]2+ is formed in the normal way, but the addition
of the fifth and sixth NH3 molecules difficult. Sixth molecules can only be added only
in liquid ammonia (Cotton and Wilkinson, 1989).
Synthesis of complex compounds can be performed by various methods,
depending on the existing system but not all methods can be used for the synthesis of
a complex. The commonly methods used in the synthesis of complex compounds is
through the substitution reaction (replacement). This method involves the reaction
between a metal salt in an aqueous solution (M n+) with the coordination agent (ligand)
in which an exchange/explacement of the ligand. For example , the manufacture of
[Cu(NH3)4]SO4 can be done by mixing a solution of CuSO 4 in water with NH3 through
the reaction :
[Cu(H2O)4]2+(aq) + 4NH3(aq) [Cu(NH3)4]2+(aq) + 4H2O(l)

Dark blue
Complex of salt [Cu(NH3)4]SO4 is dark blue crystals that is formed on the addition of
ethanol. Synthesis of complex compounds through recrystallization can be done with
some of the following techniques :
- Evaporate the solvent and cooling the reaction mixture becomes more
concentrated in a water-bath containing a salt-ice.
- Slowly add solvent that can be mixed with solvent of reaction mixture, but not
dissolving the desired compound.
- If the desired cation complexes can be isolated by adding the appropiate anion, so
it will form an insoluble salt, and instead of a cation can be added to the reaction
mixture to precipitate the anion.
(Inorganic Chemistry Lecturer Team, 2015)
C. Equipment and Material
Equipment :
1. 50 ml volumetric flask
2. 100 ml beaker
3. 1 set of vacuum pumps
4. Filter paper
5. A small test tube
6. 1 set buchner heating
7. 1 large test tube
Material :
1. Crystal of CuSO4.5H2O
2. Concentrated ammonia
3. Ethyl alcohol 96%
D. Work Instruction
1. Synthesis of tetra ammin copper(II)sulphate complex
2.5 g CuSO4.5H2O weighed and then dissolved in 5 ml H2O in a glass
beaker

12.5 ml of concentrated NH3 10% added, stirred it until homogeneous

4 ml of 96% ethyl alcohol added in the walls of the beaker. Dont be
stirred or shaken
Covered with a watch glass and allow it for 1 hour

Let stand and store it in refrigerator for overnight to crystallize

Crystals are separated by filtration

Crystals are washed with 4 ml of concentrated ammonia mixture with

ethyl alcohol (1:1)

The crystals are dried

The dry crystals are weighed
Experiment 2. Study the properties of the complex salt tetrammincoppere(II)sulphate
A little salt dissolved from step q of experiment in 5 ml H2O, the
color is observed

The solution dillute with 20 ml H2O, the color change is observed

Aof dry salt placed in a test tube and reheat slowly. The color change
is noted. Observed the gases released

E. Result of Observation
The mass of CuSO4.5H2O = 2,5 gram
Mr CuSO45H2O = 249,5
mass
n CuSO4.5H2O =
Mr
=

2.5
249.5

= 0.0100 mol
Reaction (adding water)
CuSO4.5H2O(s) + H2O(l)
m

0.0100 mol

0.0100 mol

0.0100 mol

0.0100 mol

s
0
0
Reaction (adding NH3)
Cu(H2O)4SO4(aq) + 4NH3(aq)
m
0.0100 mol
0.0400 mol
r
0.0100 mol
0.0400 mol
s
0
0
Mr Cu(NH3)4SO4 = 227,5
Cu N H 3 ) 4 ] SO 4
The theoritical mass of [ (

Cu(H2O)4SO4(aq) + 2H2O(l)
0

0.0100 mol

0.0200 mol

0.0100 mol

0.0200 mol

Cu(NH3)4SO4(aq) + 4H2O(l)
0
0
0.0100 mol 0.0400 mol
0.0100 mol 0.0400 mol
= nM
=

0.0100 mol 227.5

Rendement

= 2,2750 gram
mass of [ Cu ( N H 3 )4 ] SO 4 by experiment
= mass of [ Cu ( N H ) ] SO theoritically x 100%
3 4

1.7836
2.2750

x 100%

= 78.40%
F. Discussion
Synthesis of tetraamincopper(II) sulphate experiment has crystallization and
recrystallization methode. Crystallization is to separate by forming crystals,
recrystallization is to purify the precipitate.
1. Synthesis of tetraamincopper(II)sulphate complex
Practicant must prepare CuSO4.5H2O crystals and NH3 to synthesis it. The color
of CuSO4.5H2O is blue and it is solid, practicant must dissolve it with aquadest.
Aquadest have big dipol moment, so CuSO4.5H2O can dissolve. But it is dificult to
dissolve, it must stirring for many times. This hydrat still in one ion species. When
dissolve in aquadest, the solution has blue color. Blue color of solution because there
are Cu2+ ion. Look at this reaction :
CuSO4.5H2O(s) + H2O(l)
[Cu(H2O)4]SO4(aq) + 2H2O(l)
Based on reaction, we know that aquadest pull H 2O in crystals to form solution.
The solution will be produced [Cu(H2O)4]SO4 is a complex salts.
After that, NH3 concentrated put into the solution, this process do in acid cupboard
because NH3 concentrated will produce sting gases. The gases is dangerous for
practicant, so we need safety our self.
Stir it quickly after added NH3 and cover it by ethyl alcohols slowly. In order to
save NH3, that because of NH3 is easily to evaporate. If much NH 3 evaporate, so H2O
in [Cu(H2O)4]SO4 cant remove and opportunity for producing crystals is little. The
function of adding NH3 is to push H2O ligand. NH3 is strong ligand and H2O is weak
ligand, so NH3 can push easily. NH3 remove H2O from [Cu(H2O)4]SO4, the complex
become [Cu(NH3)4]SO4. Strong ligand make the color become more darken. The
solution after this reaction is dark blue - purple. Look at this reaction :
[Cu(H2O)4]SO4(aq) + 4 NH3 (aq)

[Cu(NH3)4]SO4(aq) + 4 H2O(aq)
Then closed with plastic, in order to the gases are not dissapear and crystals formed
maximally. We need 1 hours to waiting it. It can prevent vapourization of some ions,
and for forming monoclin crystal perfectly too.
After that the solution save in refrigerator along 3 days. Low temperature make
solubility decrease and crystals can formed. Observe the result after 3 days. There are
crystals have dark blue color. But there still little solution. To purify this solution wash
with mix solution (NH3 concentrated with ethyl alcohol). Washing solution can
increase the mass of crystals, because washing can separate crystals from another
substance.
The crystal dried use oven until dry for 15 minutes, so the result of crystals is
purify crystals not contain water or another substance. After weighing the mass of
tetraamincopper(II) sulphate are 1,7836 g. Based on theory the mass of crystals is
2,2750 g. From that data, the rendement of tetraamincopper(II) sulphate is 78,40%.
From that we know it still not maximally because occurs some mistakes, there are :
- When dissolve CuSO4.5H2O with aquadest this still not dissolve perfectly, because
in fact CuSO4.5H2O very difficult to dissolve.

Adding ethyl alcohols not enough slowly, it makes the solution not cover be
spreed evenly.
- Covering use plastic not enough quickly, so NH3 was evaporate.
2. Study the properties of the complex salt tetrammincopper(II)sulphate
The complex salt of tetraamincopper(II)sulphate has some properties. To know
that, it must test. The test has to point there are adding aquadest and heating need to
test it.
First test, aquadest 5 ml pour into the salt of tetraamincopper(II)sulphate. The
result of it is the salt dissolve and the color of solution is dark blue. Then add aquadest
20 ml, so the color of solution is light blue. Based on that we know, color of solution
become more light when we add aquadest much. They are different because there are
also different to adsorb the wave long of visible light. Only one color adsorbed, so we
can look complementer color of it. Look at this reaction :
Cu(NH3)4 SO4(s) + H2O
Cu2+(aq) + SO42-(aq) + 4NH3(g)
Second test use heating, the complex salt of tetraamincopper(II)sulphate pour into
test tube and heated. The color of salt become green.
G. Question
1. Write down all the reactions that occur in the synthesis of tetraamin copper(II)
sulphate !
2. What is the function of alcohol on the redox reaction ?
3. Mention some tetraamin copper (II) sulphate use of !
4. What type of ion that exists when tetramin copper (II) sulphate salt is dissolved in
a little water and how changes that occur when dissolved in excess water ?
5. How do the properties of this complex salt ?
Answer :
1. CuSO4.5H2O(s) + H2O(l)

[Cu(H2O)4]SO4(aq) + 2H2O(l)
[Cu(H2O)4]SO4(aq) + 4 NH3 (aq)

[Cu(NH3)4]SO4(aq) + 4 H2O(aq)
Cu(NH3)4 SO4(s) + 2H2O(l)

[Cu(H2O)2(NH3)4]2+(aq) + SO42-(aq)
2. Function of alcohol on the redox reaction is to save NH 3 in order to not evaporated,
so crystals forming.
3. Analysis forming crust in pipe
4. Cu2+ and SO425. The properties of complex salt tetraamincopper(II) sulphate in this experiment are
about adsorbtion the wave long of visible light and oxidation reaction.
H. Conclusion
1. Synthesis of tetraamincopper(II)sulphate can produce use cupri sulphate and
ammonium with the specially process (there are adding ethyl alcohols, waiting,
refrigerating, washing, and drying.
2. The properties of complex salt tetraamincopper(II) sulphate in this experiment are
about adsorbtion the wave long of visible light and oxidation reaction.
3. Rendement of [Cu(NH3)4]SO4 is 78,40 %.
I. Suggestion
1. When adding ethyl alcohols must slowly, it makes the solution covered be spreed
evenly.
2. We must covering use plastic quickly, so NH3 was not evaporate.
3. Reagents must steril from contaminated.
4. The litmus papper must keep from contaminated, so can use to know acid/base.

J. Refference
Cotton and Wilkinson. 1989. Kimia Anorganik Dasar. Jakarta: UI-Press.
Inorganic Chemistry Lecturer Team. 2015. Manual Work of Inorganic Chemistry
Practicum. Semarang : UNNES.
Sugiyarto. 2003. Dasar-dasar Kimia Anoraganik Logam. Jakarta : UI-Press
Sukardjo. 1985. Kimia Koordinasi. Jakarta: PT. Bina Aksara.
Svehla, G. 1990. Vogel : Buku Teks Analisis Anorganik Kualitatif Makro dan
Semimikro Bagian I Edisi Kelima. Jakarta: PT Kalman Media Pusaka.