Ho Chi Minh City University Of Pedagogy

Faculty: Chemistry
Department: Analytical Chemistry
Course 1050: Analytical Electrochemistry
 Chapter 1. Introduction of Electrochemical
Concepts

Electrochemistry - concerned with the interrelation of

electrical and chemical effects. Reactions involving the
reactant - the electron.

Chemical changes caused by the passage of current

An electrochemical system is not homogeneous but is

heterogeneous.

Broad Field : electroanalysis, sensors, energy storage

and conversion devices, corrosion, electrosynthesis, and
metal electroplating.
 Main Branches of Electroanalytical Chemistry

Interfacial
Bulk methods
methods

Dynamic Conductometry
Static methods (G = 1/R)
methods
(I = 0)
(I > 0)

Based on Figure 22-9 in Skoog, Holler and

Potentiometry Crouch, 6th ed.
(E) Controlled
Constant current
potential

Amperometric Electro- Coulometric

Voltammetry
titrations gravimetry titrations
(I = f(E))
(I = f(E)) (m) (Q = It)

Key to measured quantity: I = current, E = potential, R = resistance, G = conductance, Q

= quantity of charge, t = time, vol = volume of a standard solution, m = mass of an
electrodispensed species
 Electroanalytical Chemistry

Electroanalytical chemistry encompasses a group of

quantitative analytical methods that are based upon the
electrical properties of an analyte solution when it is
made part of an electrochemical cell.
These methods make possible the determination of a
particular oxidation state of an element.

Ox + ne- Red

There are two general types of electrochemical methods:

potentiometric (no current, equilibrium potential) and
voltammetric (current measured as a function of the
applied potential.
 Electrochemical Cells

Electrochemical cells consist of two electrodes: an anode

(the electrode at which the oxidation reaction occurs) and a
cathode (the electrode at which the reduction reaction
occurs).

Cu(s) + Zn2+ Cu2+ + Zn(s)

Cu(s) Cu2+ + 2e- (oxidation)
Zn2+ 2e- + Zn(s) (reduction)

There are two types of electrochemical cells: galvanic

(ones that spontaneously produce electrical energy) and
electrolytic (ones that consume electrical energy).
 Electrochemical Cells

Conduction
1. Metals
2. Solution (ion
migration)
3. Electrode rxn
(at interfaces)

A potential difference between two electrodes represents a

tendency for the reaction to occur.
 Electrochemical Potentials
The potential that develops in a cell is a measure of the
tendency for a reaction to proceed toward equilibrium.

2.303RT
o' [Ox]
EE log
nF [Re d]
Measured
E vs. Ref Nernst Equation

ax = [x]

Standard reduction reactions: all relative

to the H2/H+ reaction, 298 K, unit activities
for all species, and pH 0.
 Electrochemical Potentials

We use concentrations in the Nernst equation, but really

activities are the proper term. The activity of a species can
be defined as the ability of a species to participate an
equilibrium reaction involving itself.

e.g. Fe3+ + e- Fe2+ FeCl2+, etc.

Depends on ionic strength

Ecell = Ecathode Eanode

Grxn = -nFEcell Key equations

Grxn = -RTlnKeq
 Reference Electrodes

1. AgCl(s) + e- Ag(s) + Cl-

E = Eo + (0.059/n)log1/[Cl-]

2. Hg2Cl2(s) + 2e- 2Cl- + 2Hg(l)

E = Eo + (0.059/2)log1/[Cl-]2
Figure 22-3 A galvanic cell without a
liquid junction.

n = number of electrons transferred per mole, 2.303 RT/F = 0.059 V

 Electrochemical Cells
Voltmeter

Figure 22-5 Definition of the Stan- :

dard electrode potential for M2+(aq) + . &
2e~ ^ M(s). i

i
Cu2+ + H2(g) Cu(s) + 2H+

Zn/ZnSO4 (aZn2+ = 1.00)//CuSO4 (aCu2+ = 1.00)/Cu

Anode (oxidation) Cathode (reduction)

This shorthand is not always used in your textbook.

 Electrochemical Cells and Reactions

Electrolyte solutions (low ohmic resistance):

ionic solutions (NaCl), molten salts, and
ionic polymers (Nation).
Electrode reaction kinetics are affected by the electrode
surface cleanliness, surface microstructure, and surface
chemistry.
 Electrochemical Cells and Reactions

Two electrified interfaces but only one of interest.

V = J/C measure of the

energy available to drive
charge externally between
electrodes.

Figure 1.1.3 Schematic diagram of the

electrochemical cell Pt/HBr(l M)/AgBr/Ag attached
to power supply and meters for obtaining a current-
potential (i-E) curve.

Rate of oxidation = Rate of reduction

Reference electrode: AgBr + e- Ag + Br-(aq) E0 = 0.071V vs. NHE

Electrochemical Cells and Reactions

Magnitude of the
potential controls the
direction and rate of
charge transfer.

As a potential is moved
negative, the species
that will be reduced
first (assuming all are
rapid) is the oxidant
(acceptor) in the couple
with the least negative
Eo.
 Electrochemical Cells and Reactions

There are two types of current flow:

1. Faradaic - charge tranferred across the electrified

interface as a result of an electrochemical reaction.

dQ dN
Q nFN i nF
dt dt

2. Non-faradaic - charge associated with movement

of electrolyte ions, reorientation of solvent dipoles,
adsorption/desorption, etc. at the electrode-electrolyte
interface. This is the background current in
voltammetric measurements.
Electrochemical Cells and Reactions

Pt/H+, Br(1 M)/AgBr/Ag

Cathodic

Pt/H+, Br (1M)/AgBr/Ag

(+) current = cathodic

(-) current = anodic

(+) potential = left

(-) potential = right

Cell Potential * Anodic

Figure 1.1.4 Schematic current-potential curve for the cell Pt/H+, Br~(l A/)/AgBr/Ag, showing
the limiting proton reduction and bromide oxidation processes. The cell potential is given for the Pt
electrode with respect to the Ag electrode, so it is equivalent to En (V vs. AgBr). Since Ag/AgBr =
0.07 V vs. NHE, the potential axis could be converted to Pt (V v.s\ NHE) by adding 0.07 V to each
value of potential.

Br2 + 2 e - 2 B r - E0= 1.09 V vs. NHE

2H+ + 2e- H2 E0= 0.00 V vs. NHE

Ecell = Ec - Ea
Electrochemical Cells and Reactions
 Electrochemical Cells and Reactions

Hg/H+, Br- (1M), Cd+2(1mM)/AgBr/Ag

Hg/H+, Br(1 Ml Cd2*(1 mM}/AgBr/Ag
Current

Figure 1.1.6 Schematic current-potential curve for the Hg electrode in the cell Hg/H+,
Br~(l M),Cd2+(10~3 M)/AgBr/Ag, showing reduction wave for Cd2+.

Hg2Br2 + 2e-2Hg + 2Br- E0 = 0.14 V vs. NHE

2H+ + 2e- H2 E0= 0.00 V vs. NHE
Electrochemical Cells and Reactions
 Electrified Interfaces

Ideally polarizable electrode (IPE) - no charge transfer

across the interface. Ions move in and out of the interfacial
region in response to potential changes. The interface
behaves as a capacitor (charge storage device).

Excess electrons on one

plate and . a deficiency on
the other.
Figure 1J.1 (a) A capacitor. (b)
Charging a capacitor with a battery.
(*)

Changing the potential, E, causes the charge stored, Q,

to change according to the relationship:
Q(coulombs) = C(farads) x E(volts)
 Electrified Interfaces

qmetal = -qsolution charge neutrality!

IHR OHP
1 2 Compact Layer . = inner and outer Helmholtz planes
Diffuse layer (electrostatic forces are very strong!)
Solvated cation

Diffuse Layer = gradient of charge accumulation

(thermal agitation)

Specifically adsorbed anion

metal = qmetal/area (C/cm2)
0 = Solvent molecule

The excess charge on a metal is confined to the near surface region.

However, the balancing charge on the solution side of the interface
extends out into the solution with some thickness. (ionic zones in sol.)
Electrified Interfaces
metal = - (IHP + OHP + diffuse)

Structure of the electric double layer has

a major effect on electrode reaction
kinetics! (Faradaic reaction rates).

Species not specifically adsorbed

approach the OHP.

2 - s is wasted!!
m - s is potential felt by analyte
Figure 1.2.4 Potential profile across the
double-layer region in the absence of specific
adsorption of ions. The variable 4>, called the
inner potential, is discussed in detail in
Section 2.2. A more quantitative
representation of this profile is shown in
Figure 12.3.6.
 Electrified Interfaces

The solution side of the interface consists of a compact

layer (inner and outer Helmholtz layers) plus a diffuse layer.
Diffuse layer extends from the OHP to the bulk solution.
Ionic distribution influenced by ordering due to coulombic
forces and disorder caused by random thermal motion.

Qm + (QCL + QDL) = 0 Qm = - (QCL + QDL)

Q = CE_ (C = Farad E = voltage difference)

Q
DL = CDLA(E-Epzc) (A = area (cm2) Epzc = point of zero charge)

Smallest value dominates

1/C = 1/CCL + 1/CDL the interfacial capacitance
TOT
Electrochemical Experiment and Variables in
Electrochemical Cells

Electrode pretreatment matters a great deal!!!

 Electrochemical Experiment and Variables in
Electrochemical Cells

Electrode surface region Bulk solution

1. Mass transfer of
Electrode reactant/product to and away
from the electrode interface.
2. Electron transfer at interface.
3. Preceeding or follow-up
chemical reactions.
4. Surface processes
ne

(adsorption/desorption)

Figure 1.3.6 Pathway of a

general electrode reaction.

Working Electrode (Indicator Electrode)

Electrochemical Experiment and Variables in
Electrochemical Cells
 Mass Transport

Modes of Mass Transport

1. Migration - movement of
charged body under
influence of an electric field.
2. Diffusion - movement of
species under the influence
of a concentration gradient.
3. Convection - stirring or
Figure 1.4.1 Concentration profiles (solid lines) and diffusion layer approximation (dashed
lines), x = 0 corresponds to the electrode surface and SQ is the diffusion layer thickness. hydrodynamic transport.
Concentration profiles are shown at two different electrode potentials: (1) where CQ(X = 0)
is about C */2, (2) where CQ(X = 0) 0 and i =
Mass Transport

(t) = 2(Dt)1/2
Current-Voltage Curve Shapes

Figure 1.5.1 Effect of an irreversible

following homogeneous chemical reaction
on nemstian i-E curves at a rotating disk
electrode. (1) Unperturbed curve. (2) and (3)
Curves with following reaction at two rotation
rates, where the rotation rate for
(3) is greater than for (2).
 Chapter 2 - Thermodynamics and Potentials
Thermodynamics encompass systems at equilibrium!

Chemical Reversibility = chemical reactions associated with the

electrochemical reaction are reversible.
Pt/H2/H+, Cl-/AgCl/Ag (standard states)
Ecell = Eright- Eleft = Ec - Ea = 0.222 - 0.000 = 0.222 V
H2 + 2AgCl - 2Ag + 2H+ + 2Cl-
Thermodynamic Reversibility = Infinitesmal driving force causes
the reaction to move forward/reverse direction. Essentially at
equilibrium.
Practical Reversibility = Actual processes occur at finite rates,
therefore, they cannot proceed at true equilibrium. However,
processes can be carried out in a manner in which thermodynamic
considerations apply.
E = E0 + (2.303RT/nF) log[Ox]/[Red]
Link between E and concs. at surface. (removal of weight/slow or fast)
Thermodynamic Quantities
 Formal Potentials

Standard conditions for Eo (298 K, pH = 0, a = 1)

Non-standard conditions or conditions where the

activities of Ox and Red are affected by the medium,
then formal potentials are used, Eo.

The formal potential incorporates the standard potential

and some activity coefficients.

E = Eo + (2.303RT/nF)log[Ox]/[Red]
Eo = Eo + (2.303RT/nF)log ox/ red
 Reference Electrodes

Reversible and obeys the

Nemst Eq. (chemical and
echem).
Constant E with time.
Returns to original potential
with passage of small
currents. Figure 2.1.1 Relationship between potentials on the NHE, SCE, and absolute scales. The
potential on (jie absolute scale is the electrical work required to bring a unit positive test charge into
the conducting phase of the electrode from a point in vacuo just outside the system (see Section
2.2.5). At right is the Fermi energy corresponding to each of the indicated potentials. The Fermi
Exhibits little hysteresis with energy is the electrochemical potential of electrons on the electrode (see Section 2.2.4).

temperature cycling.

E = Eo + (2.303RT/nF) log[Ox]/[Red]
Reference Electrodes
 Electrode Potential Measurement

Two electrodes (two interfaces) are required to make a potential measurement!

Interactions Between Phases
Measurement of Potential Differences
Junction Potentials
Junction Potentials
Junction Potentials
Junction Potentials
Junction Potentials