Electrochemistry

Maisari Utami

Prof. Dr.rer.nat. Drs. Karna Wijaya, M.Eng.

1. Introduction
• Oxidation and reduction (redox) reactions occur in many chemical
systems
• Examples:
- the toasting of bread
- the rusting of iron
- the action of bleach on stains
- the production and combustion of petroleum
- generates electricity
- moves our cars
2. Galvanic (Voltaic) Cells
• The energy from a battery comes from a spontaneous redox reaction
in which the electron transfer is forced to take place through a wire.
• The apparatus that provides electricity in this way is called a galvanic
cell, after Luigi Galvani (1737–1798), an Italian anatomist who
discovered that electricity can cause the contraction of muscles.
• It is also called a voltaic cell, after another Italian scientist Allesandro
Volta (1745–1827), whose inventions led ultimately to the
development of modern batteries.
2. Galvanic (Voltaic) Cells

In the silver half-cell, the following half-reaction occurs.

In the copper half-cell, the half-reaction is

2.1 Cell Reactions
• The overall reaction that takes place in the galvanic cell is called the
cell reaction.
2.2 Naming Electrodes in a Galvanic Cell
• The electrodes in electrochemical systems are identified by the names
cathode and anode.
• The names are always assigned according to the nature of the
chemical changes that occur at the electrodes. In all electrochemical
systems:
- The cathode is the electrode at which reduction (electron gain) occurs.
- The anode is the electrode at which oxidation (electron loss) occurs.
2.3 Conduction of Charge
• For the galvanic cell to work, the solutions in both half-cells must remain
electrically neutral. This requires that ions be permitted to enter or leave
the solutions.
• The salt bridge allows the movement of ions required to keep the solutions
electrically neutral. The salt bridge is also essential to complete the
electrical circuit.
• A salt bridge is a tube filled with a solution of a salt composed of ions not
involved in the cell reaction (often KNO3 or KCl is used).
• The tube is fitted with porous plugs at each end that prevent the solution
from pouring out, but at the same time enabling the solution in the salt
bridge to exchange ions with the solutions in the half-cells.
2.4 Standard Cell Notation
• As a matter of convenience, chemists have devised a shorthand way
of describing the makeup of a galvanic cell.
Exercise 1
• The following spontaneous reaction occurs when metallic zinc is
dipped into a solution of copper sulfate.

• Describe a galvanic cell that could take advantage of this reaction.

What are the half-cell reactions? What is the standard cell notation?
Make a sketch of the cell and label the cathode and anode, the
charges on each electrode, the direction of ion flow, and the direction
of electron flow.
3. Cell Potentials
• A galvanic cell has an ability to push electrons through the external
circuit.
• The magnitude of this ability is expressed as a potential. Potential is
expressed in an electrical unit called the volt (V), which is a measure
of the amount of energy, in joules, that can be delivered per coulomb
(the SI unit of charge) as the charges move through the circuit.
• Thus, a charge flowing under a potential of 1 volt can deliver 1 joule
of energy per coulomb.
3. Cell Potentials
• The voltage or potential of a galvanic cell varies with the amount of
charge flowing through the circuit.
• The maximum potential that a given cell can generate is called its cell
potential, Ecell, and it depends on the composition of the electrodes,
the concentrations of the ions in the half-cells, and the temperature.
• The standard state for electrochemistry is defined as a system where
the temperature is 25 °C, all concentrations are 1.00 M, and any gases
are at 1.00 atm pressure.
• When the system is at standard state, the potential of a galvanic cell is
the standard cell potential, symbolized by E°cell.
3.1 Reduction Potentials
• It is useful to think of each half-cell as having a certain natural
tendency to acquire electrons and proceed as a reduction.
• The magnitude of this tendency is expressed by the half-reaction’s
reduction potential. When measured under standard conditions,
namely, 25 °C, concentrations of 1.00 M for all solutes, and pressures
of 1 atm for all gases, the reduction potential is called the standard
reduction potential.

• Thus, the standard reduction potential for the half-reaction is

specified as EoCu2+
3.1 Reduction Potentials

• Example:
3.2 The Hydrogen Electrode
• Unfortunately there is no way to measure the standard reduction
potential of an isolated half-cell. All we can measure is the difference
in potential produced when two half-cells are connected.
• Therefore, to assign numerical values for standard reduction
potentials, a reference electrode has been arbitrarily chosen and its
standard reduction potential has been defined as exactly zero volts.
• This reference electrode is called the standard hydrogen electrode
3.2 The Hydrogen Electrode
• This electrode is surrounded by a solution whose temperature is 25
°C and in which the hydrogen ion concentration is 1.00 M. The half-
cell reaction at the platinum surface, written as a reduction, is:
Standard Reduction Potentials at 25 °C
Exercise 2
• What spontaneous reaction occurs if Cl2 and Br2 are added to a
solution that contains both Cl- and Br-. Assume standard conditions.
Exercise 3
• A typical cell of a lead storage battery of the type used to start
automobiles is constructed using electrodes made of lead and
lead(IV) oxide (PbO2) and with sulfuric acid as the electrolyte. The
half-reactions and their standard reduction potentials in this system
are

• What is the cell reaction and what is the standard potential of this
cell?
Exercise 4
• A galvanic cell is constructed by placing 1.0 M aluminum nitrate in
one beaker with an aluminum electrode and a second beaker with 1.0
M copper nitrate and a copper electrode. When a salt bridge is
inserted to connect the two beakers, what cell potential do we expect
to measure between the copper and aluminum electrodes? Which
electrode is the anode and what is the spontaneous chemical
reaction?
Exercise 5
• Determine whether the following reactions, at standard state, are
spontaneous as written. If a reaction is not spontaneous, write the
equation for the reaction that is.
4. E°cell and G°
• The fact that cell potentials allow us to predict the spontaneity of
redox reactions is no coincidence.
• There is a relationship between the cell potential and the free energy
change for a reaction.

• In an electrical system, work is supplied by the flow of electric charge

created by the potential of the cell.
4. E°cell and G°
• n = the number of moles of electrons transferred
• F = Faraday constant (9.65 × 104 coulombs per mole of electrons)
• Ecell = the potential of the cell in volts.
• If, 1 volt = 1 joule/coulomb.
• Therefore:
4. E°cell and G°
• Combining Equations gives us

• At standard state we are dealing with the standard cell potential, so

we can calculate the standard free energy change.
Exercise 6
• Calculate G° for the following reaction, given that its standard cell
potential is 0.320 V at 25 °C.
4.1 E°cell and Equilibrium Constants
• One of the useful applications of electrochemistry is the
determination of equilibrium constants. In Chapter of
Thermodynamics, G° is related to the equilibrium constant by the
expression:

• Kc = equilibrium constant.

• G° is also related to E°cell

4.1 E°cell and Equilibrium Constants
• Therefore, E°cell and the equilibrium constant are also related.
Equating the right sides of the two equations, we have:

• Solving for E°cell gives:

• The value of R must be 8.314 J mol-1K-1, T must the temperature in

kelvins, F equals 9.65 × 104 C per mole of electrons, and n equals the
number of moles of electrons transferred in the reaction.
Exercise 7
• Calculate Kc for the reaction in Example 6.
5. Cell Potentials and Concentrations
• At 25 °C when all of the ion concentrations in a cell are 1.00 M and
when the partial pressures of any gases involved in the cell reaction
are 1.00 atm, the cell potential is equal to the standard potential.
5.1 The Nernst Equation
• The effect of concentration on the cell potential can be obtained from
thermodynamics.
• In Chapter of Thermodynamics you learned that the free energy
change is related to the reaction quotient Q by the equation:

• Substituting for G and G° gives:

5.1 The Nernst Equation
• Dividing both sides by -nF gives:

• This equation is commonly known as the Nernst equation, named

after Walther Nernst, a German chemist and physicist.
• Notice that if Q = 1, then ln Q = 0 and Ecell = E°cell
Exercise 8
• Suppose a galvanic cell employs the following half-reactions.

• Calculate the cell potential when [Ni2+] = 4.87 × 10-4] and [Cr3+] = 2.48
× 10-3 M.
Exercise 9
• The reaction of tin metal with acid can be written as

• Calculate the cell potential when (a) the system is at standard state,
(b) the pH is 2.00, and (c) the pH is 5.00. Assume that [Sn2+] = 1.0 M
and the partial pressure of H2 is 1.00 atm.
Exercise 10
• A laboratory was assigned the job of determining the copper(II) ion
concentration in thousands of water samples. To make these
measurements an electrochemical cell was assembled that consists of
a silver electrode, dipping into a 0.225 M solution of AgNO3,
connected by a salt bridge to a second half-cell containing a copper
electrode. The copper half-cell was then filled with one water sample
after another, with the cell potential measured for each sample. In
the analysis of one sample, the cell potential at 25 °C was measured o
be 0.62 V. The copper electrode was observed to carry a negative
charge, so it served as the anode. What was the concentration of
copper ion in this sample?
6. Electrolytic Cells
• In our preceding discussions, we’ve examined how spontaneous redox
reactions can be used to generate electrical energy.
• We now turn our attention to the opposite process, the use of electrical
energy to force nonspontaneous redox reactions to occur.
• When electricity is passed through a molten ionic compound or through a
solution of an electrolyte, a chemical reaction occurs that we call
electrolysis.
• This particular cell contains molten sodium chloride (a substance
undergoing electrolysis must be molten or in solution so its ions can move
freely and conduction can occur).
• Inert electrodes—electrodes that won’t react with the molten NaCl or the
electrolysis products—are dipped into the cell and then connected to a
source of direct current (DC) electricity.
6. Electrolytic Cells
• The DC source serves as an “electron pump,” pulling electrons away from
one electrode and pushing them through the external wiring onto the
other electrode.
• The electrode from which electrons are removed becomes positively
charged, while the other electrode becomes negatively charged.
• When electricity starts to flow, chemical changes begin to happen. At the
positive electrode, oxidation occurs as electrons are pulled away from
negatively charged ions. Because of the nature of the chemical change,
therefore, the positive electrode becomes the anode. The DC source
pumps the electrons through the external electrical circuit to the negative
electrode. Here reduction takes place as the electrons are forced onto
positively charged sodium ions, so the negative electrode is the cathode.
6. Electrolytic Cells
• The chemical changes that occur at the electrodes can be described
by chemical equations:
6.1 Comparing Electrolytic and Galvanic Cells
6.2 Electrolysis of Water in Aqueous Systems
• At the cathode, water is reduced.

• At the anode, water is oxidized, not the sulfate ion.

7. Electrolysis Stoichiometry
• In about 1833, Michael Faraday discovered that the amount of
chemical change that occurs during electrolysis is directly
proportional to the amount of electrical charge that is passed through
an electrolysis cell.
• The SI unit of electric current is the ampere (A) and the SI unit of
charge is the coulomb (C). A coulomb is the amount of charge that
passes by a given point in a wire when an electric current of one
ampere flows for one second. This means that coulombs are the
product of amperes of current multiplied by seconds. Thus:
Electrolysis Stoichiometry
Exercise 11
• How many grams of copper are deposited on the cathode of an
electrolytic cell if an electric current of 2.00 A is run through a
solution of CuSO4 for a period of 20.0 min?
Exercise 12
• Electrolysis provides a useful way to deposit a thin metallic coating on
an electrically conducting surface. This technique is called
electroplating. How much time would it take, in minutes, to deposit
0.500 g of metallic nickel on a metal object using a current of 3.00 A?
The nickel is reduced from the +2 oxidation state.
TERIMA KASIH