1.

Principles of electrochemistry: Potential & Thermodynamics

Electrochemistry is the branch of chemistry concerned with the interrelation of electrical and
chemical effects. A large part of this field deals with the study of chemical changes caused by the
passage of an electric current and the production of electrical energy by chemical reactions. Ionic
conduction (flow of ions) + electronic conduction (flow of electrons).

Electrochemical systems concern with the processes and factors that affect the transport of
charge across the interface between chemical phases, for example, between an electronic
conductor (electrodics) and an ionic conductor (ionics).

Electrodics study of reactions which occur at the surface of an electronic conductor (electrode)
in contact with a liquid. The physical chemistry of ionic solutions deals with the properties of
electrolytes such as concentrations of ions, their mobilities, interactions, etc.

Electrolyte is a substance that produces ions so enhance the electrical conductivity e.g., solid
(NaCl), liquid(H2SO4), gas (NH3) cf) solid electrolyte. Electrode is the junction between
electronic conductor and ionic conductor where the chemistry of electrochemistry occurs. Typical
electrode materials include solid metals (e.g., Pt, Au), liquid metals (Hg, amalgams), carbon
(graphite), and semiconductors (indium-tin oxide, Si). The most frequently used electrolytes are
liquid solutions containing ionic species, such as, H+, Na+, Cl-, in either water or a nonaqueous
solvent. To be useful in an electrochemical cell, the solvent/electrolyte system must be of
sufficiently low resistance (i.e., sufficiently conductive) for the electrochemical experiment
envisioned.

The basic unit of electrochemical cell is an ionic conductor sandwiched between two electronic
conductors e.g., aqueous solution of electrolyte between two pieces of metal, solid electrolyte
between two metals.

1.1. Dynamic Equilibrium

M ↔ M+Z + Ze-
 Zn/Zn2+,С-/AgCl/Ag

In this notation, a slash represents a phase boundary and a comma separates two components
in the same phase.

1.2. Electrochemical Cells

An assembly, or system, consisting of one electronic conductor (usually a metal) that acts as an
electron source for particles in an ionic conductor (the solution) and another electronic conductor
acting as an electron sink receiving electrons from the ionic conductor is known as an
electrochemical cell, or electrochemical system, or sometimes an electrochemical reactor.

These systems are defined most generally as two electrodes separated by at least one electrolyte
phase. Charge is transported through the electrode by the movement of electrons (and holes). In
the electrolyte phase, charge is carried by the movement of ions. In general, a difference in
electric potential can be measured between the electrodes in an electrochemical cell. The electron
outflow from one electronic conductor equals the inflow to the other; that is, a purely chemical
reaction (one not involving net electron transfer) can be carried out in an electrochemical cell.
The electrochemical reaction rate is the rate at which the power source pushes out and receives
back electrons after their journey around the circuit that includes the electrochemical cell.

Electrochemical cells in which faradaic currents are flowing are classified as either galvanic or
electrolytic cells. A galvanic cell is one in which reactions occur spontaneously at the
electrodes when they are connected externally by a conductor (Figure 1.3.1a). These cells are
often employed in converting chemical energy into electrical energy. Galvanic cells of commercial
importance include primary (nonrechargeable) cells (e.g., the Leclanche Zn-MnO2 cell),
secondary (rechargeable) cells (e.g., a charged Pb-PbO2 storage battery), and fuel cells (e.g., an
H2-O2 cell).

An electrolytic cell is one in which reactions are effected by the imposition of an external voltage
greater than the open-circuit potential of the cell (Figure 13.1b). These cells are frequently
employed to carry out desired chemical reactions by expending electrical energy. Commercial
processes involving electrolytic cells include electrolytic syntheses (e.g., the production of chlorine
and aluminum), electrorefining (e.g., copper), and electroplating (e.g., silver and gold). The lead-
acid storage cell, when it is being "recharged," is an electrolytic cell.

Galvanic cell: Energy is delivered by the cell into the load; ex) car: starting engine, lighting lamps

Right-hand electrode: electrons consumed; reduction, “cathode”

Left-hand electrode: electrons produced: oxidation, “anode”

1.3. Cell voltage (E) or emf (electromotive force)
Zn(M) | ZnSO4(aq, m1) || CuSO4(aq, m2) | Cu(M)

For the cell: M | M+z(aq) || N+z(aq) | N

Cell reaction: M + N+z → M+z + N

1. Write the right-hand electrode reaction as a reduction reaction:

N+z + ze- ⇔ N ............ ER
2. Write the left-hand electrode reaction as a reduction reaction:
M+z + ze- ⇔ M ..........…EL
3. Subtract right-left to get both the cell reaction and the cell emf:
Cell reaction: R-L, M + N+z →M+z + N
Cell emf: Ecell = ER–EL
The potential difference is therefore always the equilibrium (open-circuit) value
4. Then, using the relation: ΔG = -zFEcell < 0 (maximum reversible work)
G = charge passed × reversible potential difference = zFE
where z is the number of electrons passed per atom of zinc reacted (or the number of moles
of electrons per mole of Zn reacted), and F is the charge on a mole of electrons, which is
about 96500 C/mole. However, we also recognize that the Gibbs free energy change has a
sign associated with the direction of the net cell reaction. We can reverse the sign by
reversing the direction.
If Ecell > 0, cell reaction direction: L→R
if Ecell < 0, cell reaction direction: R→L

The potential difference of a cell measured at equilibrium (no current flow) and between platinum
terminals is called the electrochemotive force of the cell.
1.4. Standard Electrode Potential
The Standard electrode potential of all other electrodes is obtained by forming a cell in which the
S.H.E is on the left and the electrode under investigation in on the right. The ions and gases
involved in the second electrodes are brought to unit activity;

E°(cell) = E°R–E°L(S.H.E.) = E°R

The internationally accepted primary reference is the standard hydrogen electrode (SHE), or
normal hydrogen electrode (NHE), which has all components at unit activity:

S.H.E : H+( aH+= 1 ) | H2( f = 1 atm) , Pt

Ecell0( H / H2) = 0

2H+ + 2e- = H2

The Reversible electrode is characterized by an electrochemical reaction that can be reversed

when the electrical current changes direction;

For the case of Cu2+/Cu electrode at equilibrium,

At small anodic current: Cu →Cu2+ + 2e-

By reversing the current: Cu2+ + 2e- → Cu

Therefore, Eeq = Erev

1.5. Thermodynamics of Cell

The tendency for any chemical reaction, including corrosion, is measured by the ΔG.

Nernst Equation: For the electrochemical reaction

aA + bB → cC +dD

ΔG - ΔG°= RT ln[aproduct/areactant]

𝑐 𝑑
𝑎𝐶 ∙𝑎𝐷
∆𝐺 = ∆𝐺 0 + 𝑅𝑇𝑙𝑛 [ 𝑎 ∙𝑎𝑏 ] ; ΔG°= -zF|E°|
𝑎𝐴 𝐵

E=E°- (RT/zF) ln[aproduct/areactant] : Nernst Equation.

Consider Zn immersed in the acid solution and find the corrosion tendency of Zn;
We can’t measure the Ecell through this experiment because anodic site and cathodic site are
almost same and changes with time. The Ecell can be measured by constructing an
electrochemical cell:

Cathode
Anode

R: 2H+ + 2e- = H2

L: Zn2+ + 2e- = Zn

2H+ + Zn = H2 + Zn2+

Assuming that: aH+=1, PH2=1, aZn+2=1 for simplicity,

The standard hydrogen electrode (SHE) is chosen to have zero potential

0
𝑎𝐻2 ∙ (𝑎𝑍𝑛2+ = 1)
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − (0.059⁄2)𝑙𝑛 ( )
(𝑎𝐻+2 = 1) ∙ 𝑎𝑍𝑛

Determine whether zinc will corrode in a 0.01M ZnCl2solution acidified to pH=2. Solution:
construct an electrochemical cell corresponding to the corrosion reaction given:
1.6. Types of Cell in Corrosion
a) Galvanic cell: A potential difference exists when two dissimilar metals, electrically connected,
are immersed in a corrosive solution.
•mother phase -impurities or precipitates
•iron pipe connected to copper pipe
•annealed metal -cold worked metal
•grain -grain boundary: μgb>μM, μ⊥>μM, where μM represents the chemical potential of 1 mole
of normal atoms. In this regard, metallic glass is more corrosion resistant than is
polycrystalline metal.

b) Concentration Cells: Cells having two identical electrodes each in contact with a solution of
different concentration.
1.7. Experimental Measurements of Electrochemical Potential
The overall chemical reaction taking place in a cell is made up of two independent half-reactions,
which describe the real chemical changes at the two electrodes. Each half-reaction (and,
consequently, the chemical composition of the system near the electrodes) responds to the
interfacial potential difference at the corresponding electrode.

Most of the time, one is interested in only one of these reactions, and the electrode at which it
occurs is called the working (or indicator) electrode. To focus on it, one standardizes the other
half of the cell by using an electrode (called a reference electrode) made up of phases having
essentially constant composition.

Reference electrode: An electrode having a relatively fixed value of potential regardless of the
environment in which it is used & should have the following characteristics:

-stability

-reversible potential

-low polarizability
•The potential difference of a cell is measured when there is no flow of current and the cell is
operating reversibly. This is achieved by using a high impedance voltmeter, or potentiometer that
has a negligible input current.

•The standard hydrogen electrode (E°H+/H2=0) : the primary reference electrode

•Secondary reference electrodes are more conveniently used in the great majority of experimental
measurements.

1) The saturated calomel electrode (SCE): most popular ref. electrode for laboratory use.

2) The silver-silver chloride electrode: preferred for use at high temperature.

3) Cu-saturated CuSO4 electrode: commonly used in field.

Li-Fe Battery  Li Metal (LiB) (Reference Electrode)

Li+ + e- = Li ; 3.0 V vs Li/Li+

1.8. Potential - pH (Pourbaix) Diagrams

Also known as EH-pH diagrams, it is a two-axis graphical representation of thermodynamic and
electrochemical equilibria between metal and water, indicating thermodynamically stable phases
as a function of electrode potential and pH;

The vertical axis is labeled EH for the voltage potential with respect to the standard hydrogen
electrode (SHE) as calculated by the Nernst equation. The "H" stands for hydrogen, although other
standards may be used, and they are for room temperature only.

- predicts the spontaneous direction of reactions.

- estimates the composition of corrosion products.

- predicts environmental changes that will prevent or reduce corrosion attack.

The lines in the Pourbaix diagram show the equilibrium conditions, that is, where the activities are
equal, for the species on each side of that line. On either side of the line, one form of the species will
instead be said to be predominant.

In order to draw the position of the lines with the Nernst equation, the activity of the chemical species
at equilibrium must be defined. Usually, the activity of a species is approximated as equal to the
concentration (for soluble species) or partial pressure (for gases). The same values should be used
for all species present in the system.
For metal M immersed in the pure water (25°C) in which the metal M is divalent and forms solvated

M2+ ions and the simple oxide is MO.

Water itself is sensitive to electrode potential, decomposing to hydrogen below a potential E H2 given
by:

and decomposing to oxygen above EO2 given by:

It is evident that the increase of pressure increases the range of stability of water.

Since the reference electrode has a constant makeup, its potential is fixed. Therefore, any changes in
the cell are ascribable to the working electrode. We say that we observe or control the potential of
the working electrode with respect to the reference, and that is equivalent to observing or controlling
the energy of the electrons within the working electrode (1, 2). By driving the electrode to more
negative potentials (e.g., by connecting a battery or power supply to the cell with its negative side
attached to the working electrode), the energy of the electrons is raised. They can reach a level high
enough to transfer into vacant electronic states (lowest unoccupied molecular orbital, LUMO) on
species in the electrolyte. In that case, a flow of electrons from electrode to solution (a reduction
current) occurs (Figure a).

Similarly, the energy of the electrons can be lowered by imposing a more positive potential, and at
some point electrons on solutes in the electrolyte will find a more favorable energy on the electrode
and will transfer there. Their flow, from solution (highest occupied molecular orbital, HOMO) to
electrode, is an oxidation current (Figure b). The critical potentials at which these processes occur
are related to the standard potentials, E°, for the specific chemical substances in the system.