01-12-2016

Separation of Metals from a

Solution (Cu-Ni) Through
Electrolysis
Karen Louise de Sousa Pesse

Supervision: Christa Sonck / christa.sonck@ugent.be

Introduction
Quantitative separation of Copper and Nickel

Electrolysis is a technique used in chemistry and manufacturing to separate

elements from a solution by using a direct electric current, driving a non -
spontaneous chemical reaction.
In this practical, Copper and Nickel were separated from an aqueous solution by
their difference in equilibrium potential. This method is only possible when the
difference in equilibrium potential between substances is large enough.
For Copper and Nickel, the equilibrium potentials for reduction relative to the Standard
Hydrogen Electrode (SHE) are:
0
𝐸𝐶𝑢 2+ /𝐶𝑢 = 0,337V

0
𝐸𝑁𝑖 +2 /𝑁𝑖 = -0,24V

These values are relatively close to each other, thus it has to be handled carefully to avoid
that Nickel is deposited together with C opper on the cathode. The method of the Fixed
Cathode Potential is applied in an attempt to avoid that.
Copper precipitates in acid medium at a cathode potential of -0.60 V vs Hg/Hg 2 SO 4 .
Afterwards, Nickel deposits on the cathode in a strong ammonia medium.
1
Notice that through complexation in the form of 𝑁𝑖(𝑁𝐻3 )2+
4 the activity of the free ions
2+
Ni is lowered, and precipitation in the form of hydroxides is prevented.

Methods

The inert Platinum electrodes are thoroughly cleaned in concentrated HNO 3 and rinsed
with water. This step is fundament al to remove the traces of organic contamination from
prior metal deposition. Then, the electrode which functions as cathode is dipped in alcohol
and ether, and dried for about 5 minutes in the furnace with temperatures in the range of
100-110°C.
After cooling the electrode, this shall be weighted with an analytical balance.
Subsequently, the electrodes are attached to a DC voltage source. The cathode is
connected to a multimeter in order to measure the potential difference between cathode
and the reference electrode (Hg/Hg 2 SO 4 ).
A shunt resistor converts the measured current to voltage. The measured voltage is
written through an X (t)-recorder in a function of time. The paper moves forward at a
speed of 30mm/s.

Karen Louise de Sousa Pesse

Determination of Copper

Firstly 25 ml of Copper-Nickel solution was pipetted into the beaker, and then diluted until
the electrode was completely immersed. Thereafter 1 ml 36N H 2 SO 4 by 100 ml of solution
is added and heated at temperatures between 70 and 80°C.
The DC voltage source was set at a cat hode potential of -0.60V with respect to the
reference electrode. The movement of the electrode current recorded against the time
will be measured by X (T) recorder. When all of the copper is removed from the solution,
the electrode is weighed.

Determination of Nickel

The electrodes shall be cleaned as in the first step to remove the copper layer of the
cathode. Regarding the solution, 12 grams of (𝑁𝐻4 )2 SO 4 and 30 ml of 14N NH 4 OH were
added. Also, the solution should be diluted to 300ml and heated to 70°C.
The course of the voltage is measured by using the X (t) recorder in a function of time.
Afterwards, the cathode is weighed on the analytical balance.

Standard Cell Voltage

0
2
The standard cell voltage 𝐸𝑐𝑒𝑙 can be calculated via equation:
0
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒 (1)
Wherein the voltage of the electrodes can be found through the Nernst equation [1]:
𝑅𝑇
𝐸 = 𝐸 0 + 𝑛𝐹 ∑ 𝜈𝑖 ln 𝑐𝑖 (2)

Take R as the ideal gas constant (3,31451 J/K mol), T the temperature in Kelvin, n the
number of electrons that is exchanged, F the Faraday constant (9,6485 x 10 4 C/mol), 𝜈𝑖 the
stoichiometric numbers and 𝑐𝑖 the concentration. At room temperature, this can be
simplified to:
0,059 𝑉
𝐸 = 𝐸0 + 𝑛
𝑙𝑜𝑔[𝐶] (3)

This equation is known as Nernst equation. Considering a pure solid, the activity can be
equaled to 1.

Karen Louise de Sousa Pesse

Efficiency

The efficiency is the ratio between the measured and the theoretical maximum yield. The
theoretical yield is determined by the Faraday formula :
𝑀𝑄
𝑚= 𝐹𝑛
(4)

In this formula, M is the molar mass in g/mol and Q is the total charge in Coulombs.

Results and Questions

Complete the electrolysis schedule and enter the correct polarity (+/-) on.

Anode Cathode
3

Figure 1: Completed scheme of separation of metal by means of electrolysis indicating the polarity.

The set-up for the practicum is indicated in Figure 1. Since we have an Electrolytic cell, the
anode should have a positive polarity and the cathode should have a negative polarity. The
reaction at the anode is oxidation and in the cathode is reduction.

Explain the principle of the method of fixed cathode potential based on the
given standard potentials.

As explained before, the main idea of this method is to avoid that Nickel is deposited
together with Copper on the cathode. The standard redu ction potentials of Copper and
Nickel are relatively close to each other: 0.337 V for Copper and -0.24 V for Nickel, relative
to the Standard Hydrogen Electrode (SHE). Using a constant potential of -0.60 V relative to
an Hg/Hg 2 SO 4 reference electrode will allow the copper to precipitate separately.
The cathode is then cleaned and set up for the deposit of Nickel in strong ammonia
environment, in which the free Ni 2+ ions are complexed into 𝑁𝑖(𝑁𝐻3 )2+
4 , having their
activity reduced and preventing hydroxide precipitation. In this way, Nickel will precipitate
on the cathode in its metallic form.

Karen Louise de Sousa Pesse

The determination of Copper

Which Reactions occur at the cathode and anode? Calculate the standard cell
voltage at equilibrium.

At the cathode the reduction of Copper will happen as follow:

𝐶𝑢2+ + 2𝑒 − → 𝐶𝑢 E° = 0,337 V
And at the anode the oxidation of water will be carried:
2𝐻2 𝑂 → 𝑂2 + 4𝐻 + + 4𝑒 − E° = 1.229 V
Thus, the balanced global reaction is:
2𝐶𝑢2+ + 2𝐻2 𝑂 → 2𝐶𝑢 + 𝑂2 + 4𝐻 +
And the Standard Cell Voltage at Equilibrium according to (1) is:
0 0 0
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒 = 0,337 − 1,229 = −0,892 𝑉

Compare the standard cathode potential with the specified electrolysis

potential.

4
The standard cathode potential is the likelihood that a species will be reduced.
During the experiment there is an attempt to av oid formation of Hydrogen gas. When H 2 is
formed, an amorphous decomposition o f copper can jeopardize the experiment.
Thus the cathode potential of -0.60 V and the reference electrode Hg/Hg 2 SO 4 (E 0 =0,657 V)
are combined forming the same potential as 0,057 V relative to the Standard Hydrogen
Electrode (SHE).
In this way the potential is kept as low as possible, but still higher than 0 volts relative to
the Standard Hydrogen Electrode.

Karen Louise de Sousa Pesse

 Calculate and determine the amount of deposited copper and the concentration
of Cu2+ in the original solution. Calculate the equation potential of Cu2+/Cu in
the original solution.

During the electrolysis Oxygen gas is formed at the cathode. The copper deposition is
promptly visible, being amorphous and easy to crumble. The initial weigh of the Platinum
cathode was 35,4760 grams and the final weigh was 35,5994 grams.
The amount of deposited Copper is then :
𝑚𝐶𝑢 = 𝑚𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒 𝑎𝑓𝑡𝑒𝑟 − 𝑚𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒 𝑏𝑒𝑓𝑜𝑟𝑒 = 35,5994𝑔 − 35,4760𝑔 = 0,12 𝑔𝑟𝑎𝑚𝑠

With this information, and the molar mass of copper being 63,54 g/mol, the concentration
of copper ions in 200 ml of solution is determined by:
𝑚𝐶𝑢 1 0,12𝑔 1 𝑚𝑜𝑙
𝐶𝐶𝑢2+ = = = 0,00944
𝑀𝑀𝐶𝑢 𝑉 63,54𝑔/𝑚𝑜𝑙 0,2𝑙 𝑙
To calculate the equation potential of Cu 2+ /Cu in the original solution, the Nernst equati on
(3) shall be used:
𝟎, 𝟎𝟓𝟗 𝑽
𝑬 = 𝑬𝟎 + 𝒍𝒐𝒈[𝑪]
𝒏
0 0,059 V 0,059 V 35,5994𝑔 − 35,4760𝑔 1 5
𝐸𝑐𝑎𝑡 = 𝐸𝐶𝑢 2+ /𝐶𝑢 + log(𝐶𝐶𝑢2+ ) = 0,337 V + log ( ) = 0,278 𝑉
2 2 63,54𝑔/𝑚𝑜𝑙 0.2𝑙
To calculate the Nernst equation for anode potential, the concentration of Hydrogen ions
shall be determined. This value can be obtained from the addition of 2 ml of H 2 SO 4 (18M)
to 200 ml of solution:

(2𝐶𝐻2 𝑆𝑂4 𝑉𝑎𝑑𝑑𝑒𝑑 ) (2 ∗ 18 𝑀 ∗ 0,002 𝑙)

𝐶𝐻 + = = = 0,36 𝑀
𝑉𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 0,2 𝑙
It is important not to forget about the factor 2 in the previous equation, since there are
two ions H + for each H 2 SO 4 .
The potential of the anode will then be:
4
0,059 0,059 (2 ∗ 18 𝑀 ∗ 0,002 𝑙)
𝐸𝑎𝑛𝑜𝑑𝑒 = 𝐸𝑂02 /𝐻2 𝑂 + log(𝐶𝐻4 + ) = 1,229 + log { } = 1,2028 𝑉
4 4 0,2 𝑙
The experimental cell potential stands for:
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒 = 0,278 − 1,2030 𝑉 = −0,925 𝑉

Karen Louise de Sousa Pesse

 Why does the measured cathode potential differ from this value?

The measured value for E c a t ho de was 0,837 V. This value is obtained in the beginning of the
experiment, before the electrolysis starts. The system voltage is 0,180 V and Hg/Hg 2 SO 4
which is used as reference electrode has a potential of 0,657 V. The measured cathode
potential is then 0,180 + 0,657 = 0,837 V.
The difference in values can be blamed to the fact that a Platinum electrode was used. The
potential of Platinum during reduction reaction equals 1,2 volts . This creates a discrepancy
caused by the measurement of the reduction of platinum as well.

Calculate the efficiency of the copper electrolysis based on the course of the
electrolysis current in function of the time.

After the end of the experiment, the area underneath the I (t) curve mad e was calculated.
A value of 517,68 C was obtained. This value is then used in the Faraday law (4) in order to
calculate the amount of copper deposited in an ideal case:
𝑔
𝑀𝑄 𝑀𝑀𝑐𝑜𝑝𝑝𝑒𝑟 1 63,54 1
𝑚𝑐𝑜𝑝𝑝𝑒𝑟 = = ∗ ∫ 𝐼(𝑡) = 𝑚𝑜𝑙 517,68 𝐶 = 0,170 𝑔
𝐹𝑛 2 96500 𝐶/𝑚𝑜𝑙 2 𝐶
96500
𝑚𝑜𝑙
To obtain the efficiency of the electrolysis:
𝑚𝑐𝑜𝑝𝑝𝑒𝑟𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑 0,12 𝑔
𝐸𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 𝜼 = ∗ 100% = ∗ 100% = 70% 6
𝑚𝑐𝑜𝑝𝑝𝑒𝑟𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑 0,170𝑔
𝑖𝑑𝑒𝑎𝑙

The determination of Nickel

Which reactions occur at the cathode and anode? Calculate the standard-cell
voltage at equilibrium.

At the cathode, the reduction of Nickel will happen:

0
𝑁𝑖(𝑁𝐻3 )4 + 2𝑒 − → 𝑁𝑖 + 4𝑁𝐻3 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 = −0,24 𝑉
-
Meanwhile at the anode there is the oxidation of OH :
0
4 𝑂𝐻 − → 𝑂2 + 2𝐻2 𝑂 + 4 𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒 = 0,401 𝑉
The balanced global reaction corresponds to:
2 𝑁𝑖(𝑁𝐻3 )4 + 4 𝑂𝐻 − → 2𝑁𝑖 + 8 𝑁𝐻3 + 𝑂2 + 2 𝐻2 𝑂
Thus, the Standard-Cell Voltage at Equilibrium is:
0 0 0
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒 = −0,24𝑉 − 0,401 𝑉 = −0,641 𝑉

Karen Louise de Sousa Pesse

 Calculate the amount of deposited nickel and the concentration of Ni2+ in the
original solution. Determine, based on that concentration, the equilibrium
potential of Ni2+/Ni in the original solution.

The cathode was weighted before and after the experiment, presenting an initia l mass of
35,4759 grams and a final mass of 35,5342 grams.
The amount of deposited Nickel is then:
𝑚𝑁𝑖 = 𝑚𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒 𝑎𝑓𝑡𝑒𝑟 − 𝑚𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒 𝑏𝑒𝑓𝑜𝑟𝑒 = 35,5342𝑔 − 35,4759𝑔 = 0,0583 𝑔𝑟𝑎𝑚𝑠

It is then possible to calculate the concentration of Nickel from a solution of 300 ml,
knowing that the molar mass of Nickel is 58,71 g/mol:
𝑚𝑁𝑖 1 0,0583 𝑔 1 𝑚𝑜𝑙
𝐶𝑁𝑖2+ = ∗ = 𝑔 ∗ = 3,31 ∗ 10−3
𝑀𝑀𝑁𝑖 𝑉𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 58,71 0,3𝑙 𝑙
𝑚𝑜𝑙
Subsequently, the cathode potential shall be calculate from the Nernst equation:
𝟎, 𝟎𝟓𝟗 𝑽
𝑬 = 𝑬𝟎 + 𝒍𝒐𝒈[𝑪]
𝒏

0 0.059 0.059
𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 = 𝐸𝑁𝑖 +2 /𝑁𝑖 + log(𝐶𝑁𝑖2+ ) = −0.24 𝑉 + log(3,31 10−3 ) = −0,313 𝑉
2 2
7
-
To calculate the anode potential, the concentration of OH shall be determined. Taking
into consideration 30 ml of 14M NH 4 OH into a diluted solution of 300 ml, this solution
being saturated with H + from previous experiment:
𝑉𝑎𝑑𝑑𝑒𝑑 0,03𝑙
𝐶𝑂𝐻− = 𝐶𝑁𝐻4 𝑂𝐻 𝑉 = 14 𝑀 ∗ 0,30𝑙 = 1,4M
𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

(𝑤𝑖𝑡ℎ𝑜𝑢𝑡 𝑖𝑛𝑓𝑙𝑢𝑒𝑛𝑐𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑎𝑐𝑖𝑑)

0,20𝑙
𝐶𝐻+ = 0,36 𝑀 → 200 𝑚𝑙 = 0,26 𝑀 ∗ → 300 𝑚𝑙 = 0.24 𝑀 𝑖𝑛 300 𝑚𝑙
0,30𝑙
𝐶𝑂𝐻− = 1.4 𝑀 − 0.24 𝑀 = 1.16 𝑀
(𝑤𝑖𝑡ℎ 𝑖𝑛𝑓𝑙𝑢𝑒𝑛𝑐𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑎𝑐𝑖𝑑)
0.059 0,03𝑙 0,20𝑙
𝐸𝑎𝑛𝑜𝑑𝑒 = 𝐸𝑂02 /𝑂𝐻− − 4 −)
log(𝐶𝑂𝐻 = 0.401 𝑉 − 0.059 log (14 𝑀 ∗ − 0,26 𝑀 ∗ ) = 0,3972 𝑉
4 0,30𝑙 0,30𝑙
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒 = −0,313 𝑉 − 0,3972 𝑉 = −0,7102 𝑉

Karen Louise de Sousa Pesse

Calculate the efficiency of the nickel electrolysis based on the course of the
electrolysis current in function of time.

After the end of the experiment, the area underneath the I (t) curve mad e was calculated.
A value of 711,232 C was obtained. This value is then used in the Faraday law (4) in order
to calculate the amount of nickel deposited in an ideal case:
𝑔
𝑀𝑄 𝑀𝑀𝑁𝑖𝑐𝑘𝑒𝑙 1 58,71 1
𝑚𝑁𝑖𝑐𝑘𝑒𝑙 = = ∗ ∫ 𝐼(𝑡) = 𝑚𝑜𝑙 711,232 𝐶 = 0,2163 𝑔
𝐹𝑛 2 96500 𝐶/𝑚𝑜𝑙 2 𝐶
96500
𝑚𝑜𝑙
The efficiency will then be:
𝑚𝑛𝑖𝑐𝑘𝑒𝑙𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑 0.0726 𝑔
𝐸𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 𝜼 = ∗ 100% = ∗ 100% = 33,56%
𝑚𝑛𝑖𝑐𝑘𝑒𝑙𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑 0.2163𝑔
𝑖𝑑𝑒𝑎𝑙

Karen Louise de Sousa Pesse

Conclusion

Compare the performance of the copper electrolysis and explain the difference.
Declare in the same connection, also the difference in view of the current
curves in both cases.

Electrolysis is a suitable method to purify Copper, and it is often applied in industry.

Comparing with the copper electrolysis one can clearly see that nickel electrolysis is a lot
less efficient.
This is visible on the I(t) curve and can be explained by the fact that durin g the Nickel
electrolysis more ions can be found in the solution, resulting in a higher rate of side
reactions if compared to the copper electrolysis. In a real environment, ammonium sulfate
is a strong acidic salt ammonium hydroxide is a weak base, making room for ionizations
with many by-products causing higher viscosity during the nickel deposition, which may
affect the reaction negatively.
The reason you can notice this behavior in the I(t) curve is because the high amount of
ions in the solution containing Nickel will increase the transfer of electrons, which affects
the Faraday equation:
𝑀𝑄
𝑚𝐸𝑙𝑒𝑚𝑒𝑛𝑡 =
𝐹𝑛
This all leads to a low efficie ncy and higher residual current, culminating in a curve that
9
ends further from 0 amperes during the nickel electrolysis.

References

[1] Christopher M. A. Brett. Electrochemistry: principles, methods, and applications.

Oxford science publications. Oxford University Press, 1993. isbn: 0198553897.

Annex - I (t) curves

Due to the shunt resistance, the voltage of 20 mV is associated with a current of 8

amperes. Thus, on the graph, the range of current will vary between -4 A and 4A.

Karen Louise de Sousa Pesse