Democratic and Popular Republic of Algeria

Ministry of Higher Education and Scientific Research

Benyoucef Benkhedda University, Algiers 1

Faculty of Science B3 Analytical Chemistry

Department of Materials Science 2023/2024

PW N° 04: Water Electrolysis (the intensity-potential curves)

I. Overview
Green hydrogen is a renewable hydrogen produced using water electrolysis technology and electricity
generated from renewable energy sources, such as solar or wind. It is a key element in accelerating the
shift to clean energy. The commercialization of electrolyzers can make green hydrogen more readily
available and enable energy systems around the world to undergo fundamental transformations to reduce
emissions and reduce their negative impact on the environment. So what is the electrolysis of water?

I.1. Definitions
Water electrolysis is an electrolytic process that breaks down water into oxygen and hydrogen gas using
an electric current. In other words, the electrolysis of water is one of the methods of synthesizing
dihydrogen molecules according to the following reaction.

2H2O (l) → 2H2 (g) + O2 (g)

An electrolyzer is a generator that converts the electrical energy into a chemical energy.

I.2 The composition of an electrolyzer.

As depicted in the figure bellow, an electrolysis cell consists of two electrodes, namely the anode and
cathode, which are connected to a direct current (DC) power supply. These electrodes are separated or
immersed by an electrolyte, which acts as an ionic conductive medium.

PW Electrochemical analysis methods Prepared by Dr. H. BOUCHAREB and Dr. F. HADJI

 Fig. I. 1. Schematic representation of an electrolyzer.

I.3. Electrochemical reactions in water electrolysis

During the process of water electrolysis in an alkaline medium, two reactions occur: the hydrogen
evolution reaction (HER) and the oxygen evolution reaction (OER).

4OH- (aq) → O2 (g) + 2H2O (L) + 4e-………………(OER)

4H2O (L) + 4e- → 2H2 (g) + 4OH- (aq) ……………(HER)

I.4. Intensity-potential curves

The plot of the intensity-potential curve consists of following the evolution of the current intensity as a
function of the applied potential (I = f (E)).

 If the generator is not supplying voltage, no current will flow through the electrodes: they will therefore
be at a potential, known as the "equilibrium potential", such that Nernst's formula can be verified.
 If the voltage at the generator terminals is gradually increased, a current i will flow through the circuit.

In order to distinguish the phenomena involved at the anode and the cathode surfaces, we use the
following convention for drawing the curves:
If the electrode studied is the anode, the current intensities are counted positively.
If the electrode studied is the cathode, the current intensities are counted negatively.

To measure the current intensity i(mA) of the electrode studied as a function of the applied potential E
(V), we use a three-electrode system comprising:

• A working electrode (the one being studied);

• A reference electrode (Ag/AgCl in general)
• A counter electrode allowing the passage of current (Pt in general).

PW Electrochemical analysis methods Prepared by Dr. H. BOUCHAREB and Dr. F. HADJI

 We impose a potential on the working electrode by varying the potential difference and we measure the
value of its potential E in relation to the reference electrode as well as the intensity of the current which
circulates between the working electrode and the counter electrode. To have an electrochemical reaction,
the potential must deviate from equilibrium by a value called the overvoltage η and defined generally by:

η = 𝐸 - 𝐸eq

With this definition, we see that we predict:

 if η = 0 (𝐸 = 𝐸eq), no reaction will happen.
 if η > 0 (𝐸 > 𝐸eq), it is an oxidation reaction.
 if η < 0 (𝐸 < 𝐸eq), it is a reduction reaction.

Note; ηa the anodic overvoltage (always positive) and ηc the cathodic overvoltage (always negative).

Fig. I. 2. Polarization curves of the hydrogen and the oxygen evolution reactions in an alkaline medium.

II. Objective:
In this laboratory session, we will demonstrate how to construct an electrolysis cell, how to determine
the polarity of its electrodes, and how to plot and interpret the intensity-potential curves.

PW Electrochemical analysis methods Prepared by Dr. H. BOUCHAREB and Dr. F. HADJI

III. Experimental section:
III.1. Equipment and solutions

The equipment and solutions needed to carry out the dosage are:
 Electrolysis tank or a beaker (~200 mL).
 Platinum electrode
 Reference electrode (Ag/AgCl)
 Graphite electrode or nickel plate
 Voltage generator
 A voltmeter.
 An ammeter.
 Connecting wires.
 A solution of potassium hydroxide (C = 2M).

III.2. Operating procedure

 Pour about 50 ml of potassium hydroxide solution into the beaker.
As, depicted bellow;
 Insert the reference electrode equidistant between the two platinum electrodes.
 Connect the two electrodes (RE/WE) to the terminals of a voltage generator.
 Connect the two electrodes (CE/WE) to the terminals of ammeter.
 Connect the two electrodes (RE/WE) to the terminals of a voltmeter.

 Turn on the generator to start electrolysis of water.

 As shown in the table below, gradually increase the voltage (V) and measure the intensity I (mA).

Eapp (V) 0.0 0.05 0.1 0.15 0.2 0.25 0.30 0.35 0.4
imeas (mA)
Eapp (V) 0.45 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9
imeas (mA)

PW Electrochemical analysis methods Prepared by Dr. H. BOUCHAREB and Dr. F. HADJI

Questions
 Put the results in a table.
 Plot and interpret the intensity-potential curve.
 Indicate in the diagram bellow:
 The direction of the electric current in the circuit?
 The direction of movement of the electrons in the circuit outside the electrolyzer.
 The direction of movement of cations (positive ions) and anions (negative ions) within the
solutions.
 The positive terminal and the negative terminal of the electrolyzer.
 The anode and the cathode.

 Specify the electrode which is the site of; an oxidation reaction and reduction reaction.
 Deduce from all the observations made previously the equation of the reaction which occurs at each of
the electrodes.
 Determine the reaction equation that describes the overall operation of the electrolyzer.

PW Electrochemical analysis methods Prepared by Dr. H. BOUCHAREB and Dr. F. HADJI