Volume No.

Issue No.2

August 6, 2014

Electrogravimetric Determination of Cobalt, Copper and Nickel from Mixture

ABSTRACT
Electrogravimetry is a method to determine the amount of metal present in the analyte using electroplating at the
electrode. This experiment aimed to apply electrogravimetric technique in determining the amount of metal in
aqueous solutions of their divalent salts and to separate metals from its mixture. The chlorine ion of the salts NiCl 2,
CuCl2 and CoCl2 were removed and reagents such as H2SO4 and NH4OH were added to produce analytes of pure Ni,
Cu and Co, and mixture of Ni-Cu and Co-Cu. These were subjected to Eberbach Electroanalyzer where the change
in weight of electrodes was equal to the amount of metal after electroanalysing with the aide of air and oven drying.
The amount of pure Ni and Cu were observed near to their actual value while the amount of Cu in the mixture was
greater than the actual value. After performing the experiment, the two purposes were obtained.

INTRODUCTION
Electroanalytical chemistry is composed of methods
that are based upon the electrical properties of a
solution of the analyte when it is made part of an
electrochemical cell.
Electrogravimetry is one of the two electroanalytical
methods. The product of electrogravimetry is
deposited quantitatively on an electrode by an
electrolytic reaction and the amount of product is
determined by weighing the electrode before and
after electrolysis. Electroplating is done at the
negative electrode or the cathode, where reduction
takes place. When the electrode gains weight, the
amount of the metal can be calculated. The goal of
electrogravimetry is to electroplate 100% of the
desired analyte of the solution.
There are two types of electrogravimetry; controlledpotential and controlled-current. In controlledpotential, the potential at the electrode is kept
constant while plating out all the analyte. The current
decreases as the metal is plated out. This type is
effective when 2 or more metals are plated out where
the metal ion that is more easily reduced can be
plated out quantitatively without the involvement of
the other. In controlled-current, large amount of
voltage is needed to sustain a constant current to flow
throughout the cell.

As for this experiment, electrogravimetry is

recommended as the quickest and one of the most
precise methods of determination of Co, Ni and Cu in
aqueous solution of their divalent salts.
This experiments purposes are to apply
electrogravimetric technique in determining the
amount of metal in aqueous solutions of their
divalent salts and to separate metals from its mixture.

EXPERIMENTAL SECTION
The reagents used were 85% hydrazine hydrate,
concentrated H2SO4 and NH4OH, CuCl2, NiCl2 and
CoCl2 samples. The main instrument used was the
Eberbach Electroanalyzer. For the solution to be
prepared, the glasswares and apparatus used were
pipet, beakers, thermometer, watch glass, stirring rod,
wash bottle, Bunsen burner and hot plate.

Professor, School of Che-Chm, Mapa Institute of Technology

Student, CHM115L/A11, School of Che-Chm, Mapa Institute of Technology

finally, to light blue having a white solid. Heating

was continued for 5 to 10 minutes to assure complete
removal of chloride ion. Upon complete removal, the
solution was diluted with 100 mL distilled water and
the electrolysis was carried out.

Figure 1. Eberbach Electroanalyzer

Figure 2. Reagents used

First, the platinum electrodes were immersed in nitric

acid for few minutes. It was then washed with
distilled water and rinsed with several small portions
of acetone, and was dried in an oven at 110C for 2 to
3 minutes. After cooling, it was ready for electrolysis.
The first assigned sample was Cu in aqueous CuCl2.
The sample was placed in a 100 mL electrolytic
beaker. 2.3 mL of concentrated H2SO4 was slowly
added. Upon addition of H2SO4, brown and white
precipitates were formed with evolution of fumes.
The mixture was placed in a hotplate and heated to
near boiling. During initial heating, the brown and
white solids were dissolved leaving a green solution.
The solution turned pale green after 2 minutes. 1 mL
of HNO3 was added while the solution was pale
green. Subsequently, the solution turned from pale
green to blue green, blue green to light blue, and

The second assigned sample was Co in aqueous

CoCl2. In order to prepare the analyte, 5 mL of the
sample was placed in 100 mL beaker. 4.1 mL of
concentrated H2SO4 was added slowly. Fumes were
evolved and the solution changed color from red to
blue and blue to purple or blue with pink solid. The
mixture was placed in hot plate and heated to boiling
or until the solid change from yellow to white to light
green. The condensate was removed by flaming the
sides using the Bunsen burner. After the color change
was observed, the solution was heated for 10 more
minutes. When the entire chloride ion was removed,
the mixture was diluted using 65 mL distilled water,
36 mL of concentrated NH4OH, and 0.5 mL of 85%
hydrazine hydrate. The solution was transferred to
250 mL beaker and was heated to 70C. The
electrode was weighed to determine its initial weight.
Then analyte was subjected to the electroanalyzer.
After 5 minutes in the electroanalyzer, the device was
turned off and the electrode was air dried. The
electrode was washed with distilled water. Drops of
absolute ethanol were also used to wash the electrode
which was oven dried after. When the electrode is
fully dried, it was weighed. The electrode was
washed using a special cleaning solution. The process
for electroanalyzer was repeated until the mass of the
platinum electrode after oven drying is the same as
with its initial weight.
The third assigned sample was Ni in aqueous NiCl2.
In order to prepare the analyte, 5 mL of the sample
was placed in 100 mL beaker. 4.1 mL of concentrated
H2SO4 was added slowly. A yellow precipitate
formed. The mixture was placed in hot plate and
heated to boiling or until the solid change from
yellow to white to light green. The condensate was
removed by flaming the sides using the Bunsen
burner. After the color change was observed, the
solution was heated for 5 more minutes. The mixture
was diluted using 65 mL distilled water and 35 mL of
concentrated NH4OH. The solution was transferred to
250 mL beaker and was heated to 70C. The
electrode was weighed to determine its initial weight.

Then analyte was subjected to the electroanalyzer.

After 5 minutes in the electroanalyzer, the device was
turned off and the electrode was air dried. The
electrode was washed with distilled water. Drops of
absolute ethanol were also used to wash the electrode
which was oven dried after. When the electrode is
fully dried, it was weighed. The electrode was
washed using a special cleaning solution. The process
for electroanalyzer was repeated until the mass of the
platinum electrode after oven drying is the same as
with its initial weight.

Figure 3. Heating the solutions

RESULTS AND DISCUSSION

Table 1-Single Metal
Element
Cu
Co
Ni

Average wt. of
metal
0.616 0.0135
0.1827 0.1537
0.616 5.0576
x 10-3

Average time
consumed
30 1.6859
35.84 11.23
30 1.6859

Figure 5. Copper before electrolysis

Figure 4. Drying the electrodes

In the separation of metals, the procedure in

preparing aqueous solution of metals was followed.
The two metal solutions assigned, Cu-Ni and Cu-Co,
were combined. The electrolysis was performed by
varying the current applied. The current used in
copper is 1 Ampere, in cobalt is 2 Amperes, and in
nickel is 2 Amperes also. The results were then
gathered and interpreted.

Figure 6. Cobalt before electrolysis

%
error
4.6%
74%
3.2%

Table 2-Combine Metal

Element
Cu-Ni
Cu-Co

Figure 7. Nickel before electrolysis

After heating, the copper solution became light blue,

the cobalt solution became violet, and the nickel
solution became dark blue. The analytes containing
the pure samples were electroanalyzed thrice. The
average weight acquired in nickel is 0.4023 g, in
copper is 0.1827, and in Cobalt is 0.616.
The reduction of Nickel can be shown as:
Ni2+ + 2e- Ni Eo cell = -0.250 V
The reduction of Copper can be shown as:
Cu2+ + 2e- Cu Eo cell = 0.3402 V
The reduction of Cobalt can be shown as:
Co2+ + 2e- Co Eo cell = -0.277 V
The mass of the empty electrode is 63.448 g. these
are combined small and large electrodes. The current
used in copper is 1 Ampere, while in both nickel and
cobalt is 2 Amperes. The acquired percentage error
for nickel is approximately 4.6%, for copper is 74%,
and for cobalt is 3.2%. The error for copper was
observed to be greater than the accepted range, 0% to
10%. One factor that might have affected this is the
involvement of the small values. Another factor is the
incomplete dryness of the electrode when weighed.
Some drops of ethyl alcohol might have stayed in the
electrode which caused gain in weight. It may also be
the instrumental errors or human errors. Low
percentage errors of nickel and cobalt indicate very
good results.

Average wt. of
metal
0.168 0.094
0.3243 0.4561

Average time
consumed
30.32 1.997
29 1.6859

%
error
76%
54%

Another analyte contained the mixture of 2 mL Cu2+

and 3 mL Ni2+, 2 mL Cu2+ and 3 mL Co2+. After
heating the solution, the color of Cu-Co and of CuNickel is bright pink and bright blue. After, triple
electrolysis, the color darkens because the metals
were adhered to the electrodes.
Here, we were unable to weigh the amount of nickel
and cobalt in the solution. The weights indicated in
table 2 are only the weights of copper in the solution.
The percent errors were too high that might indicate
that other chemicals have affected the process of
electroanalysis. As for my opinion, the electrode
might not be thoroughly oven dried which caused the
overweightness of the metal. Another factor to be
considered is the procedure for the assigned mixture
since its components varied by volume and by group.
The procedure was unclear on the color change and
to what indicator will the heating stop. But the major
mistake here is the unable separation of nickel and
cobalt to the solution. We admit that we lack
knowledge of the procedure that causes such mistake.
The current in the system can be used to determine
the mass of the metals through this equation:
Q = It = nFN

CONCLUSION
After performing the experiment, the two objectives
were successfully obtained. For the first objective,
the researcher had successfully measured the amount
of nickel, copper, and cobalt present in the respective
analytes which were close to the true value of the
metal. The amounts of Nickel-Copper and CobaltCopper were also measured though the percent errors
are very high due to some sources such as confusion
in procedure and incomplete drying. For the second
objective, the metals in mixture were separated by

electroplating cobalt, followed by nickel, then

copper.
It is highly recommended that the salts of the metal
must have high concentration in order to observe the
expected outcome. The procedures must also be
revised since the combination of the metals varies
depending on the group.

REFERENCES
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(1998) Principles of Instrumental Analysis, 5th Ed.,
Thomas Learning, Inc.
2. Skoog, D. A., Holler, F. J., West, D. M., and
Crouch, S. R. (2011) Fundamentals of Analytical
Chemistry, 8th Ed., Cengage Learning.
3. Owen, J. F., Patterson, C. S., and Rice, G. S.
(1983), Electrogravimetric Determination of Cobalt,
Nickel and Copper in Presence of Chlorine Ion,
Analytic Chemistry, 990-992, ACS Publication.
4. Skoog, D. A., Holler, F. J., and Crouch, S. R.
(2011) Principles of Instrumental Analysis, 6th Ed.,
Thomas Learning, Inc.
5. Habib, M. A. (1988) Electrogravimetric
characterization of the electrochromic polyaniline
film surface, Langmuir, 1302-1304, ACS Publication.
Website:
1.

http://staff.tanta.edu.eg/uploads/unit_5_electrogr
avimetry_and_coulometry.pdf