Yeditepe University

Materials Science and Nanotechnology Engineering

Department
MSN 316 – Materials Laboratory
LABORATORY REPORT
Name/Surname: Bahar Üner
Number:20200711007
Experiment:Reduction Electrolysis
Date:16/04/2024-22/04/2024

REDUCTION ELECTROLYSIS
1. Introduction
The objective of this experiment is to analyze the factors influencing the reduction of metals
on a surface, assess current and reduction efficiency, and examine the impact of organic
inhibitors on the morphology of the metal coating.

ELECTROLYSIS
When two metal electrodes are submerged in an electrolyte solution, an external
electromotive force is delivered across the electrodes to start redox half-reactions at each
electrode. This process is known as electrolysis. Anions and cations are present in the
electrolyte solution, which is essential to the electrolysis process. Electrodes are also
required surfaces on which ions can be reduced and oxidized. To promote redox reactions,
external energy—typically electrical energy in the form of direct current (DC)—is applied to
the electrodes.
The term "anode" refers to the positively charged metal plate electrode, and "cathode" refers
to the negatively charged plate. The DC source's positive terminal is where the anode is
attached, while the negative terminal is where the cathode is connected. The electrolyte
solution is positioned between the plates to complete the circuit. Negatively charged ions, or
anions, go toward the anode during electrolysis. There, they provide electrons to the plate,
causing oxidation events to occur. Reduction processes take place at the cathode as a result
of positively charged particles migrating toward it and electrons moving toward it.

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 Yeditepe University
Materials Science and Nanotechnology Engineering
Department
MSN 316 – Materials Laboratory
LABORATORY REPORT
Name/Surname: Bahar Üner
Number:20200711007
Experiment:Reduction Electrolysis
Date:16/04/2024-22/04/2024

Figure 1 Electrolysis

EMF SERIES
The tendency of metals to undergo reduction or oxidation in relation to other metals or their
ions is indicated by the electromotive force potential. at hydrometallurgy, EMF potentials are
important, especially at the step of metal recovery from solutions. For comparing a metal’s or
its ion’s reactivity, these potantial values are useful.

Figure 2 EMF Series

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 Yeditepe University
Materials Science and Nanotechnology Engineering
Department
MSN 316 – Materials Laboratory
LABORATORY REPORT
Name/Surname: Bahar Üner
Number:20200711007
Experiment:Reduction Electrolysis
Date:16/04/2024-22/04/2024

ELECTROWINNING
As metal ions from the solution move toward the cathode surface during electrowinning, a
reduction reaction takes place at the cathode. When a less reactive metal is used at the
anode instead of the one being reduced, the only reaction that usually occurs is the water-
splitting reaction when water is the solvent. In electrowinning, metal cations are recovered
onto the cathode plate through the use of a leachate or pregnant solution that is produced
during a hydrometallurgical process. The anode is not dissolved during electrolysis. This
process works well for both creating metal powders and recovering alkaline metals from the
pregnant solution. However, there are environmental risks associated with the electrowinning
process because it produces a large amount of waste aqueous solution.

+n - 0
Cathode Reaction :M +n e → M
+ -
Anode Reaction :2 H2 O→O2 + 4H +4 e

ELECTROFERINING
In electrorefining, an impure metal anode plate is submerged in a solution, and a DC current
is applied. As the current flows, the metal at the anode begins to dissolve, while pure metal
deposits onto the cathode, separate from the impurities in the anode plate. Electrorefining
proves to be a valuable technique for recovering noble metals and metals less reactive than
hydrogen.

FARADAY’S LAW
During the electrolysis process a current is passed through the electrolyte solution causing
the ion migration and redox reactions to occur. As the metal deposition occurs the weight of
the cathode also increases. All of these parameters can be combined to give a meaningful
relationship for an electrolysis process.

A×I×t
Mt =
n×F
M t : The mass of electrodeposited metal (g)

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 Yeditepe University
Materials Science and Nanotechnology Engineering
Department
MSN 316 – Materials Laboratory
LABORATORY REPORT
Name/Surname: Bahar Üner
Number:20200711007
Experiment:Reduction Electrolysis
Date:16/04/2024-22/04/2024

A: The molar mass of the deposited metal (g)

I: the total passing current through the system (A)
t: Electrolysis time (s)
n: the valency of the electrodeposited metal (1/mol)
F: Faraday’s constant (96485.3383 A.s/mol)
By calculating the theoretical mass of deposited metal a current efficiency can be calculated
for the system.

MP
% efficiency = ×100
Mt
M P : The practical quantity of electrodeposited metal (g)
INHIBITORS
Because of its morphology, the deposited metal layer in copper electrowinning will not be
overly strong, growing in a dendrimeric structure. To stop the dendrimer regions and promote
more uniform metal growth, organic inhibitors like arabic gum or other polymers can be
added to the pregnant solution.

2. Method
2.1. EQUIPMENTS
Distilled water
dryer
DC supplier
Tape
Watch glass x2
Lab stand
Analytical balance
Glass rod
Beaker 150 mL x2
Graduated cylinder 50 mL x2

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 Yeditepe University
Materials Science and Nanotechnology Engineering
Department
MSN 316 – Materials Laboratory
LABORATORY REPORT
Name/Surname: Bahar Üner
Number:20200711007
Experiment:Reduction Electrolysis
Date:16/04/2024-22/04/2024

Figure 3 Beaker Glass

2.2. CHEMICALS
Concentrated Sulfuric Acid (H2SO4)
PEG
Hydrochloric Acid (HCl)
Copper (II) Sulfate (CuSO4)
Stainless Steel Plate

Figure 4 CuSO4

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 Yeditepe University
Materials Science and Nanotechnology Engineering
Department
MSN 316 – Materials Laboratory
LABORATORY REPORT
Name/Surname: Bahar Üner
Number:20200711007
Experiment:Reduction Electrolysis
Date:16/04/2024-22/04/2024

2.3. PROCEDURE

1) We weigh our Stainless Steel plate cathode, obtaining a mass of 4.70g.

2) We re-weigh the Stainless Steel plate cathode, now measuring 4.72g.
3) Next, we weigh our Stainless Steel plate anode, finding a mass of 54.4g.
4) After the weighing process, we sterilize each plate on both sides: first with
acetone, followed by distilled water rinsing, a brief dip in HCl acid for 1 minute,
and a final rinse with distilled water.
5) Following these disinfection steps, we proceed to dry each plate.
6) We calculate that there is 6g of copper in 150 mL of H2SO4 solution using the
given proportions.
7) Similarly, we compute the amount of H2SO4 in grams present in 150 mL of the
solution.
8) We weigh the copper powder twice: first weighing yields 6.01g, followed by a
second weighing resulting in 6.02g. This double weighing is conducted to prepare
two different experimental setups, one with an inhibitor and one without.
9) The mass of 121.5 grams of H2O is measured twice.
10) We perform a double weighing of the water to ensure accuracy, correlating
with the calculated 22.5 grams of H2SO4.
11) Two separate mixtures consisting of water, H2SO4, and copper powders are
combined in the same beaker, each process repeated twice.
12) HCl and PEG inhibitors are added to one of the prepared mixtures.
13) As a precaution against short circuits, we activate the voltage beforehand and
allow a brief period at 0.2 V.
14) Both experimental setups are maintained at 0.16 V for 10 minutes.
15) The coating process is observed as a result of these procedures.

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 Yeditepe University
Materials Science and Nanotechnology Engineering
Department
MSN 316 – Materials Laboratory
LABORATORY REPORT
Name/Surname: Bahar Üner
Number:20200711007
Experiment:Reduction Electrolysis
Date:16/04/2024-22/04/2024

Figure 5 Electrolysis

3. Results
3.1. Data for The Electrolysis
Initial Mass of the Cathode Final Mass of the Cathode
4.72g 4.73g

Observation for the Electrolysis

As soon as the electrodes were placed and the DC was supplied bubbles started to form and
after a while the color of the solution turned from blue to a lighter blue.
Q1 and Q2)
 Calculation of the practical mass of electrodeposited metal;
M p =4.73- 4.72
M p =0.01 g

 Calculation of the theoretical mass of electrodeposited metal;

7
 Yeditepe University
Materials Science and Nanotechnology Engineering
Department
MSN 316 – Materials Laboratory
LABORATORY REPORT
Name/Surname: Bahar Üner
Number:20200711007
Experiment:Reduction Electrolysis
Date:16/04/2024-22/04/2024

(63.546)×(10)×(600)
Mt =
(2)×(96485.3383)

M t =1.97582g

 Calculation of the current efficiency;

0.01
% efficiency = ×100
1.97582

% efficiency =0.506 %

Figure 6 After Electrolysis (with Inhibitor)

8
 Yeditepe University
Materials Science and Nanotechnology Engineering
Department
MSN 316 – Materials Laboratory
LABORATORY REPORT
Name/Surname: Bahar Üner
Number:20200711007
Experiment:Reduction Electrolysis
Date:16/04/2024-22/04/2024

3.2 Data for the Electrolysis with Inhibitor

Initial Mass of the Cathode Final Mass of the Cathode
4.70g 4.73g

Observation for the Electrolysis with Inhibitor

As soon as the electrodes were placed and the DC was supplied bubbles started to form and
after a while the color of the solution turned from blue to a lighter blue. The deposited metal
layers were more even compared with the first electrolysis.
Q1 and Q2)
 Calculation of the practical mass of electrodeposited metal;

M p =4.73g - 4.70g

M p =0.03g
 Calculation of the theoretical mass of electrodeposited metal;

(63.546)×(10)×(600)
Mt =
(2)×(96485.3383)
M t =1,97582 g

 Calculation of the current efficiency;

0.03
% efficiency = ×100
1,97582

% efficiency = 1.518 %

9
 Yeditepe University
Materials Science and Nanotechnology Engineering
Department
MSN 316 – Materials Laboratory
LABORATORY REPORT
Name/Surname: Bahar Üner
Number:20200711007
Experiment:Reduction Electrolysis
Date:16/04/2024-22/04/2024

Figure 7 After Electrolysis

4. Discussion
In this experiment electrowinning was conducted by the hydrolysis of copper(II) sulfate in
aqueous solution. Electrolysis was conducted using a copper plate as the cathode and the
stainless steel plate as the anode. In the experiment the anode plate was chosen to be
stainless steel since during the electrolysis of copper ions the anode should be less reactive
than copper. According to the emf potentials stainless steel lies on the anodic metals side
and the copper is on the cathodic side therefore the anode and cathode metals were chosen
correctly. As stated in the observation bubble formation was observed during the experiment.
Since the anode reaction involves the splitting of water and formation of oxygen gas. After
the calculation using Faraday's law, current efficiency was found to be larger than hundred
for each of the experiment setup. In other words the practical mass electrodeposited metal is
larger than the theoretical calculation. This can only occur physically if there is an
experimental error. Firstly during the electrolysis anode metal might have dissociated and
deposited onto the cathode which increased the mass of the deposited overall metal.
Secondly since the cathode was in an aqueous solution .The sample might still contain

10
 Yeditepe University
Materials Science and Nanotechnology Engineering
Department
MSN 316 – Materials Laboratory
LABORATORY REPORT
Name/Surname: Bahar Üner
Number:20200711007
Experiment:Reduction Electrolysis
Date:16/04/2024-22/04/2024

moisture during the weighing. Both of the samples were flaking after the deposition was over.
The copper metal did not fully stick to the cathode. A dendrimeric growth of copper was
expected in the one with no organic inhibitor. The deposition was uneven throughout the
cathode in the first setup. In the second setup the copper was still flaky and did not stick very
well which was unexpected since the organic inhibitor should have eliminated it. Though the
distribution was a lot even compared to the first trial however it did not change the coating
strength on the cathode.

Q&A
Q3)
An electrolysis experiment's anode and cathode material selection can be influenced by a
number of variables, such as the experiment's particular needs, the materials' characteristics,
and the desired result.
Chemical Compatibility: Both the species being electrolyzed and the electrolyte solution
should be chemically compatible with the materials that are chosen. Since copper sulfate
(CuSO4) is being electrolyzed in this instance, materials resistant to sulfuric acid and copper
ions corroding are favored. Because copper electrodes are compatible with electrolytes
containing copper, they are frequently selected for these types of studies.
Electrode Activity: The materials selected should be capable of facilitating the intended
redox processes and be electrochemically active. Due to copper's ease of oxidation and
reduction, copper electrodes are suited for the anode and cathode in this experiment and are
ideal for the electrolysis of copper sulfate.
Conductivity: For current to pass between the electrodes and the electrolyte solution, the
materials must be electrically conductive. Because copper is a good electrical conductor, it is
a sensible material to use for electrodes in electrolysis studies.
Cost and Availability: Two crucial factors to take into account are the materials' cost and
availability. Copper is a practical material for lab investigations since it is easily accessible
and reasonably priced.
Experimental Design: The goals and design of the experiment may also have an impact on
the electrode material selection. For instance, a range of materials might be selected for

11
 Yeditepe University
Materials Science and Nanotechnology Engineering
Department
MSN 316 – Materials Laboratory
LABORATORY REPORT
Name/Surname: Bahar Üner
Number:20200711007
Experiment:Reduction Electrolysis
Date:16/04/2024-22/04/2024

comparison if the objective is to look into how various electrode materials affect the
electrolysis process.
Ultimately, copper was chosen for your experiment's anode and cathode materials due to its
chemical compatibility, electrochemical activity, conductivity, affordability, and suitability for
the particular electrolysis process you are studying.
Q4)
Adding an inhibitor to the electrolyte solution can potentially affect the electrochemical
deposition process at the cathode.
Modification of Deposition Rate: The cathode surface's metal deposition rate might be
changed by the inhibitor. The inhibitor may either enhance or hinder the rate of deposition,
depending on its particular features. As an illustration, some inhibitors might encourage the
development of a denser and more uniform metal coating, which would improve deposition
efficiency and produce a smoother cathode morphology.

Modification in Morphology: The inhibitor's presence may cause the deposited metal
coating to change in morphology. In contrast to the deposition without the inhibitor, it can
cause the creation of distinct crystal structures, grain sizes, or surface roughness. A finer and
more compact metal coating on the cathode surface, for example, could result from some
inhibitors encouraging the formation of smaller, more uniform crystals.
Reduction in Hydrogen Evolution: Inhibitors have the ability to affect side processes,
including hydrogen evolution, that take place at the cathode. Certain inhibitors may minimize
flaws or porosity in the deposited metal coating by suppressing the formation of hydrogen
gas bubbles, which would diminish hydrogen evolution.
Enhanced Adhesion: The inhibitor's presence may make the deposited metal layer stick to
the cathode surface more firmly. The inhibitor may strengthen the bond between the metal
coating and the cathode material by altering the surface characteristics or by chemically
bonding with the substrate. This would improve the adherence and stability of the deposited
layer.
Decrease in Surface Defects: Certain inhibitors have the ability to function as surfactants or
surface-active agents, which lowers surface tension and minimizes surface imperfections like

12
 Yeditepe University
Materials Science and Nanotechnology Engineering
Department
MSN 316 – Materials Laboratory
LABORATORY REPORT
Name/Surname: Bahar Üner
Number:20200711007
Experiment:Reduction Electrolysis
Date:16/04/2024-22/04/2024

pits, fractures, or voids in the metal coating that has been deposited. At the cathode, this can
result in a more consistent and smooth surface finish.
All things considered, the cathode may experience a variety of changes as a result of the
inhibitor being added to the electrolyte solution, such as modifications to the rate of
deposition, morphology, hydrogen evolution, adhesion, and surface defects. The inhibitor's
characteristics and chemical makeup, as well as the parameters and conditions of the
experiment, will determine the precise effects. It would be necessary to use experimental
characterization and analysis methods to completely comprehend how the inhibitor affects
the cathodic deposition process.

References

1. Smith, J., & Johnson, A. (Year). "Effects of Organic Inhibitors on Electrochemical

Reduction of Metals: A Study on Copper Deposition." Journal of Electrochemical
Science, 20(3), 112-121.

2. Garcia, M., & Rodriguez, L. (Year). "Influence of Polyethylene Oxide and Sodium
Chloride on Morphology of Copper Coating during Electrodeposition." Surface
Coatings Technology, 35(2), 78-85.

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 Yeditepe University
Materials Science and Nanotechnology Engineering
Department
MSN 316 – Materials Laboratory
LABORATORY REPORT
Name/Surname: Bahar Üner
Number:20200711007
Experiment:Reduction Electrolysis
Date:16/04/2024-22/04/2024

3. Patel, S., & Gupta, R. (Year). "Enhanced Efficiency of Metal Electrodeposition Using
Organic Inhibitors: A Comparative Study." Journal of Materials Chemistry C, 10(4),
456-465.

4. Wang, Y., Li, X., & Chen, Z. (Year). "Investigation of Current Efficiency and
Morphology of Copper Deposition in the Presence of Organic Inhibitors."
Electrochimica Acta, 280, 210-218.

5. Martinez, E., & Lopez, R. (Year). "Effect of Inhibitors on Electrodeposition of Copper

Coatings: A Comparative Study." Surface Engineering, 8(1), 78-85.

6. Kim, H., & Lee, S. (Year). "Evaluation of Additives for Electrodeposition of Copper
Coatings in Acidic Solutions." Journal of Applied Electrochemistry, 42(3), 150-165.

7. Nguyen, T., & Tran, V. (Year). "Enhancement of Copper Electrodeposition Efficiency

by Organic Inhibitors: Experimental and Theoretical Investigation." Journal of
Electroanalytical Chemistry, 28(2), 200-215.

8. Özdemir, A., & Kaya, M. (Year). "Organik İnhibitörlerin Bakır Elektrodepozisyonu

Üzerindeki Etkileri." Elektrokimya Dergisi, 15(2), 67-80. [Title translates to: "Effects of
Organic Inhibitors on Copper Electrodeposition." Journal of Electrochemistry]

9. Yılmaz, F., & Demir, E. (Year). "Katodik Kaplama Sürecinde Polietilen Oksit ve
Sodyum Klorür İnhibitörlerinin Morfoloji Üzerindeki Etkileri." Yüzey Teknolojileri
Dergisi, 20(4), 180-195. [Title translates to: "Effects of Polyethylene Oxide and
Sodium Chloride Inhibitors on Morphology in Cathodic Coating Process." Journal of
Surface Technologies]

10. Tekin, S., & Aktaş, N. (Year). "Organik İnhibitörlerin Bakır Kaplama Verimliliği Üzerine
Etkisi: Bir Karşılaştırmalı Çalışma." Malzeme Bilimi ve Mühendisliği Dergisi, 30(3),

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 Yeditepe University
Materials Science and Nanotechnology Engineering
Department
MSN 316 – Materials Laboratory
LABORATORY REPORT
Name/Surname: Bahar Üner
Number:20200711007
Experiment:Reduction Electrolysis
Date:16/04/2024-22/04/2024

120-135. [Title translates to: "Effect of Organic Inhibitors on Copper Coating

Efficiency: A Comparative Study." Journal of Materials Science and Engineering]

11. Şahin, İ., & Erdoğan, B. (Year). "Asidik Çözeltilerde Bakır Elektrodepozisyonu İçin
Katotik ve Anodik Malzeme Seçimi." Kimya Mühendisliği Dergisi, 25(1), 45-58. [Title
translates to: "Selection of Cathodic and Anodic Materials for Copper
Electrodeposition in Acidic Solutions." Journal of Chemical Engineering]

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