ELECTROCHEMISTRY BASICS

• Introduction
• Galvanic cells
• Cell potentials
• Nernst equation
• Metallic corrosion
• Summary

Introduction to Electrochemistry
Introduction
Connection between CHEMISTRY & ELECTRICITY.

 Alessandro Volta discovered, in 1793, that electricity could be produced by placing two
dissimilar metals on opposite sides of a moistened paper.
 Nicholson and Carlisle, in 1800, using Volta’s primitive battery as a source, showed that
an electric current could decompose water into oxygen and hydrogen (first proof that
water is composed of hydrogen and oxygen).

Volta and his “artificial electrical organ” William Nicholson, discoverer

of electrolysis of water

Who’s who in electrochemistry: http://www.corrosion-doctors.org/Who's_who.htm

Introduction to Electrochemistry
Introduction
Electroneutrality.
(bulk mater cannot have a chemically-significant imbalance of positive and negative ions.)
 A piece of Zn immersed in water:
Zn(solid)Zn2++2e

 The build-up of negative charge in the metal (and positive charge in the solution) soon
brings the process to a halt.
 The only way we can get the oxidation of the metal to continue is to couple it with some
other process that restores electroneutrality to the two phases. For example, immerse Zn
in a solution of CuNO3 instead of pure water. The excess electrons can be removed from
the Zn by Cu ions that come into contact with it:
Cu2++2eCu(solid)
Then, the dissolution of the Zn is no longer inhibited by a buildup of negative charge in the
metal. And the reaction becomes oxidation-reduction process.

Introduction to Electrochemistry
Introduction to Electrochemistry
Introduction Helmholtz plane 1
Metal plane MGouy plane 2

Potential differences at interfaces

hydrated cations

chemisobed anion

metal
water in normal structure
=78.5
the first water layer
=6
the second water layer
=32

Potential difference is almost entirely located across the very thin electric double layer (10 -8cm).

 Electrochemistry is the study of reactions in which charged particles (ions or electrons)

cross the interface between two phases of matter, typically a metallic phase (the
electrode) and a conductive solution (electrolyte).
 A process the reactions is known as electrode process (or electrode reaction).
 Potential differences can be related to the thermodynamics and kinetics of electrode
reactions.
 Interfacial potential differences are not directly observable.

Introduction to Electrochemistry
Galvanic cells and electrodes
Galvanic cell (voltaic cell).

Net reaction is oxidation of zinc by copper(II) ions:

Zn(s) + Cu2+  Zn2+ + Cu(s)

Half reactions take place in separate locations:

 Left electrode: Zn(s)  Zn2+ + 2e oxidation
 Right electrode: Cu2+ + 2e Cu(s) reduction

Electrochemical cells allow measurement and control of a redox (reduction/oxidation) reaction. Also,
we can force the reaction to proceed in its non-spontaneous, or reverse direction by connecting a
source of current to the two electrodes.

To sustain the cell reaction, the charge carried by the electrons through the external circuit must be
accompanied by a compensating transport of ions between the two cells.

Introduction to Electrochemistry
Galvanic cells and electrodes
Transport of charge within the cell.

 For the cell to operate, not only must there be an external

electrical circuit between the two electrodes, but the two
electrolytes must be in contact. Otherwise, violations of
electroneutrality would make the process to a halt.
 To sustain the cell reaction, the charge carried by the
electrons through the external circuit must be accompanied
by a compensating transport of ions between the two cells.
 Relative amounts of charge can be carried by negative or
positive ions (depends on their relative mobilities) through
the solution.

 Salt bridge, consists of an intermediate compartment filled

with saturated salt solution and fitted with porous barriers at
each end, is used for precise measurements. The purpose
of salt bridge is to minimize the natural potential difference
(junction potential).

Introduction to Electrochemistry
Galvanic cells and electrodes
Cell description conventions.  Single vertical bar represent phase boundary.
 Double bar denotes liquid-liquid boundary.
 Reduction process is always shown on the right.
Zn(s)│Zn2+(aq)││Cu2+(aq)│Cu(s)
Pt(s)│Fe3+(aq),Fe2+(aq)││….. , half cell reaction would be Fe2+(aq)  Fe3+(aq)+e

Electrode & electrode reactions.

Electron transfer at an anode

The energy required to displace water

molecules from the hydration shell of an
ion as it approaches the electrode surface
constitutes an activation energy.

 Metal-metal ion electrode

 Ion-ion electrode (electrode reaction involving only ion species)
 Gas electrode (reaction involving a gaseous species)
 Insoluble-salt electrode
_for example: AgCl(s)+eAg(s)+Cl-(aq), half cell:…││Cl-(aq)│AgCl(s) │Ag(s))

Introduction to Electrochemistry
Galvanic cells and electrodes
Standard hydrogen
electrode,
Reference electrode. (H+/H2 potential)

 All measurements in a electrochemical

experiment should be on a complete cell
involving two electrode systems.
 Commonly a reference electrode is
employed as the other half electrode.
 The major requirements of a reference
electrode are that it be easy to prepare
and maintain, and that its potential be
stable (can be held at a fixed value).

Potential scales of the most commonly used

reference electrodes.

Introduction to Electrochemistry
Cell potential
Cell potentials & the electromotive series.

 Some metals are more “active” than others in the sense that a more active metal can “displace” a
less active one from a solution of its salt.
 A more active metal will donate electrons to the cation of a less active metal.

The most active (most strongly

reducing, or strong tendency to
lose electrons) metals appear
on top.

Introduction to Electrochemistry
Cell potential
Standard half-cell potentials.

 Each half-cell has associated with it an electrode-solution potential difference.

 To express them in a uniform way, we adopt the convention that half-cell potentials are always
defined for the reduction direction. Thus, the half-cell potentials are always defined for the reduction
direction: Zn2++2eZn(s).
 For a net reaction such as Zn(s) + Cu 2+Zn2++Cu(s), we define the cell potential: Ecell=Eright-Eleft,
which is just the difference between the two half-cell potentials.
 The fact is that individual half-cell potentials are not directly measurable. If we adopt a reference
half-cell (hydrogen half-cell operated under standard conditions of 1 atm H 2 pressure, 25oC, and
pH=0, standard hydrogen electrode, SHE) whose potential is arbitrarily defined as zero, then we can
measure the potential of an electrode system (half-cell potential) against this reference cell.

Cell potential and Gibbs free energy.

 Potential difference (E0) between the electrodes of a cell is a measure of the tendency for the cell
reaction.
 Standard free energy G0 change expresses the tendency for any kind of process to occur under
the conditions of constant temperature and pressure.
 G0 and E0 measure the same thing, and are related in a sample way:
G0=-nFE0
 The reaction can proceed spontaneously only if the cell potential is positive ( G0 negative).

Introduction to Electrochemistry
Nernst equation

How cell potentials depend on concentrations.

 For a generalized equation of the form: aA+bB+….→mM+nN+……

Reaction quotient:

As we know for a chemical reaction, free energy changes: G=Go+RTLnQ, and G and E are
related in: G=-nFE

Therefore we have: or

Very important Nernst equation which relates the cell potential to the standard potential and to the
activities of the electroactive species.
 The Nernst equation accurately predicts only when the equilibrium quotient term Q is expressed in
activities ac, (, activity coefficient)
 In those reactions in which H+ or OH– ions take part, the cell potential will also depend on the pH.
Plots of E vs. pH showing the stability regions of related species are very useful means of
summarizing the redox chemistry of an element.

Introduction to Electrochemistry
Nernst equation

Cell potentials & pH: stability diagrams (Pourbaix diagram).

 Example 1: stability diagram for water and example 2: simple view of Pourbaix diagram for Fe

oxygen evolution
and acidification
water
therm
odyn
amica
lly sta
ble

hydrogen evolution
and alkalization

Corrosive region: the most stable form is the metal cation or any non
protective anion corrosion will occur until the metal is consumed.
Immune region: corrosion is thermodynamically impossible
Passive region: an insoluble protective layer (hydroxide or oxide layer)
is the most stable form; initial corrosion will occur until a protective layer
is formed.
Introduction to Electrochemistry
Nernst equation

Cell potentials & pH: stability diagrams (Pourbaix diagram).

 Example 2: stability diagram for iron (little bit complicated).

Horizontal lines: reactions are

involved with electrons (potential),
but independent of pH (H(+a) or OH(-a) ions):
Fe2+=Fe3++e
Ee=0.771+0.0591·lg(aFe3+/aFe2+)
Fe=Fe2++2e
Ee=0.771+0.0591·lg(aFe3+/aFe2+)

Vertical lines: reactions are

involved with pH, but independent of electrons:
Fe3++H2O=FeOH2++H+
lg(aFeOH2+/aFe3+)=-2.22+pH
Fe2++2H2O=Fe(OH)2+2H+
lg(aFe2+)=13.37-2pH

Diagonal lines: reactions are

involved both pH and electrons:
Fe2++H2O=FeOH2++H++e
Ee=0.877-0.0591pH+0.0591·lg(aFe(OH)2+/aFe2+)
Fe2++3H2O=Fe(OH)3+3H++e
Ee=0.748-0.1773pH-0.0591·lgaFe2+
Fe+2H2O=Fe(OH)2+2H++2e
Ee=-0.045-0.0591pH Introduction to Electrochemistry
 Metallic corrosion

mechanism of metallic corrosion – HOW?

Graphical representation of the pitting.

A corrosion system can be regarded as a short-

circuited electrochemical cell in which the
The bottoms of these pits tend to be
reaction takes place at anodic areas:
deprived of oxygen, thus promoting further
M(s)→M2+(aq)+2e growth of the pit into the metal.
and the cathodic process can be any of
O2+2H2O+4e→4OH-
2H++2e→H2
M2++2e→M(s)

Handbook of Corrosion Engineering, Pierre R. Roberge, McGraw-Hill

Introduction to Electrochemistry
Metallic corrosion

Thermodynamics depending on the given environmental

conditions – HOW FAR?

 While the E-pH diagram provides no

kinetic information whatsoever, it defines
the thermodynamic boundaries for
important corrosion species and reactions.

Introduction to Electrochemistry
 Metallic corrosion

Kinetics – HOW FAST?

 Electrode kinetic principles have to be used to

estimate reaction rates.

Graphical representation of the processes

occurring at an electrochemical interface.

Introduction to Electrochemistry
Metallic corrosion

Kinetics at equilibrium: the exchange current concept

 The exchange current Io is a fundamental characteristic of electrode behavior that can be defined
as the rate of oxidation or reduction at an equilibrium electrode expressed in terms of current. An
important kinetic parameter.
 There is no theoretical way of accurately determining the exchange current for any given system.
IT IS DETERMINED EXPERIMENTALLY.
Kinetics under polarization
 Electrodes can be polarized by the application of an external voltage or by the spontaneous
production of a voltage away from equilibrium. This deviation from equilibrium potential is called
polarization.
 The magnitude of polarization is usually described as an overvoltage ( ), which is a measure of
polarization with respect to the equilibrium potential (Eeq) of an electrode.
 Three distinct types of polarization in any electrochemical cell:

ηtotalE applied Eeq ηact  ηconc iR

act: activation overpotential, a complex function describing the charge transfer kinetics of the
electrochemical process.
concconcentration overpotential, a function describing the mass transport limitations associated with
electrochemical processes.
iR: ohmic drop. iR follows Ohm’s law and describes the polarization that occurs when a current
passes through an electrolyte or through any other interface such as surface film, connectors, and so
forth. Introduction to Electrochemistry
Metallic corrosion

Calculation for activation polarization – Butler-Volmer Equation

_derived from Nernst Equation.

 c ( 0 ,t ) c ( 0 ,t ) 
i  i 0  Ox b exp nf   Rd b exp1   nf ) 
 cOx cRd 
i: current density, i0: exchange current density.
: overpotential.
COx(0,t) and CRd(0,t): concentrations of oxidant and reductant at the electrode surface at time t.
COxb and CRdb: bulk concentrations of oxidant and reductant.
: transfer coefficient (or charge transfer barrier), can range from zero to unity, usually =0.5.
f=F/RT, F: Faraday; R: gas constant; T: absolute temperature.

 For sufficiently small , |nf|<<1:

i   i 0 nf
 For large values of , one of the bracketed terms in above equation becomes negligible, then we
can get a relation of the Tafel form, =a+blogi, b: Tafel slope, an important kinetic parameter.

2.303RT 2.303RT
  logi 0  logi
( 1   ) nF ( 1   ) nF

Introduction to Electrochemistry
Metallic corrosion

Calculation for concentration polarization.

– Fick’s law, Nernst-Einstein equation, etc.

The ohmic drop is caused by the electrolytic resistance between

two electrodes.
– Ohmic overpotential is a simple function described by the product of the effective solution
resistance and the cell current, or iR.

Introduction to Electrochemistry
 Metallic corrosion

Corrosion of 9Cr ODS in supercritical water – example.

6-week exposed 9Cr ODS in supercritical water at 500 oC

 When the oxide film is formed, the ion diffusion and migration will perform through this film.
 The existence of potential difference between two sides of the film (about nm level), which is about
0.* to several volts, makes the electric field intensity higher than 10 6~107 V/cm.

Introduction to Electrochemistry
Summary
Electroneutrality.
Electric double layer and potential differences at interfaces.
Galvanic cells.
Electrodes and electrode reactions.
Nernst equation.
Stability diagram (Pourbaix diagram).
Kinetics at equilibrium and under polarization (exchange current
density, Tafel slope, activation overpotential, concentration
overpotential, ohmic drop, etc).

Introduction to Electrochemistry