Electrochemical Analysis

Potentiometry,
Voltammetry,
Amperometry,

Applications
Study Redox Chemistry
electron transfer reactions, oxidation, reduction,
organics & inorganics, proteins
Adsorption of species at interfaces

Electrochemical analysis
Measure the Potential of reaction or process
E = const + k log C (potentiometry)
Measure the Rate of a redox reaction; Current (I)
= k C (voltammetry)
Electrochemical Synthesis
Organics, inorganics, materials, polymers

Electrochemical Cells
Galvanic Cells and Electrolytic Cells
Galvanic Cells power output; batteries
Potentiometric cells (I=0) read Chapter 2
measure potential for analyte to react
current = 0 (reaction is not allowed to occur)
Equil. Voltage is measured (Eeq)

Electrolytic cells, power applied, output meas.

The Nernst Equation
For a reversible process: Ox + ne- Red
E = Eo (2.303RT/nF) Log (ared/aox)
a (activity), related directly to concentration

Voltammetry is a dynamic method

Related to rate of reaction at an electrode

O + ne = R,

Eo in Volts

I = kA[O] k = const. A = area

Faradaic current, caused by electron transfer
Also a non-faradaic current forms
part of background current

Electrical Double layer at Electrode

Heterogeneous system: electrode/solution interface

The Electrical Double Layer, es in electrode; ions in
solution important for voltammetry:
Compact inner layer: do to d1, E decreases linearly.
Diffuse layer: d1 to d2, E decreases exponentially.

Electrolysis: Faradaic and Non-Faradaic Currents

Two types of processes at electrode/solution interface
that produce current
Direct transfer of electrons, oxidation or reduction
Faradaic Processes. Chemical reaction rate at electrode
proportional to the Faradaic current.
Nonfaradaic current: due to change in double layer when E
is changed; not useful for analysis

Mass Transport: continuously brings reactant from the bulk

of solution to electrode surface to be oxidized or reduced
(Faradaic)
Convection: stirring or flowing solution
Migration: electrostatic attraction of ion to electrode
Diffusion: due to concentration gradient.

Typical 3-electrode
Voltammetry cell
Reference electrode

Counter
electrode

Working electrode

O
e-

O
Mass transport

R
End of Working electrode

R
Bulk solution

Reduction at electrode
Causes current flow in
External circuit

Analytical Electrolytic Cells

Use external potential (voltage) to drive

reaction
Applied potential controls electron energy
As Eo gets more negative, need more energetic
electrons in order to cause reduction. For a
reversible reaction:
Eapplied is more negative than Eo, reduction will
occur
if Eapplied is more positive than Eo, oxidation will
occur
O + ne- = R Eo,V electrode reaction

 Current Flows in electrolytic cells

Due to Oxidation or reduction
Electrons transferred
Measured current (proportional to reaction rate,
concentration)

Where does the reaction take place?

On electrode surface, soln. interface
NOT in bulk solution

Analytical Applications of Electrolytic Cells

Amperometry
Set Eapplied so that desired reaction occurs
Stir solution
Measure Current

Voltammetry
Quiet or stirred solution
Vary (scan) Eapplied
Measure Current
Indicates reaction rate
Reaction at electrode surface produces concentration gradient with
bulk solution
Mass transport brings unreacted species to electrode surface

Cell for voltammetry, measures I vs. E

wire
potentiostat
insulator

electrode
material

reference
N2
inlet

counter

working electrode

Electrochemical cell

Output, I vs. E, quiet solution

Input: E-t waveform

E, V

time

reduction

Polarization - theoretical
Ideally Polarized Electrode

Ideal Non-Polarized Electrode

reduction

No oxidation or reduction
oxidation

Possible STEPS in electron transfer processes

Charge-transfer may be rate limiting

Rate limiting step may be mass transfer

Rate limiting step may be chemical reaction

Adsorption, desorption or crystallization polarization

Overvoltage or Overpotential
= E Eeq; can be zero or finite
E < Eeq < 0
Amt. of potential in excess of Eeq needed to
make
a non-reversible reaction happen, for example
reduction

Ee
q

NERNST Equation: Fundamental Equation for reversible

electron transfer at electrodes
O + ne- = R,
Eo in Volts
E.g., Fe3+ + e- = Fe2+
If in a cell, I = 0, then E = Eeq
All equilibrium electrochemical reactions obey the
Nernst Equation
Reversibility means that O and R are at equilibrium at all times, not all
Electrochemical reactions are reversible
E = Eo - [RT/nF] ln (aR/aO) ;
aR = fRCR

a = activity

ao = foCo f = activity coefficient, depends on ionic strength

Then E = Eo - [RT/nF] ln (fR/fO) - [RT/nF] ln (CR/CO)
F = Faraday const., 96,500 coul/e, R = gas const.
T = absolute temperature

Ionic strength I = zi2mi,

Z = charge on ion, m = concentration of ion
Debye Huckel theory says log fR = 0.5 zi2 I1/2
So fR/fOwill be constant at constant I.
And so, below are more usable forms of Nernst Eqn.
E = Eo - const. - [RT/nF] ln (CR/CO)
Or
E = Eo - [RT/nF] ln (CR/CO); Eo = formal potential of O/R
At 25 oC using base 10 logs
E = Eo - [0.0592/n] log (CR/CO); equil. systems

Voltammetric Methods
Voltammetry are based on measurement of current as a function of the potential
applied to a small electrode. Unlike potentiometry measurements, which employ
only two electrodes, voltammetric measurements utilize a three electrode
electrochemical cell. The use of the three electrodes (working, auxiliary, and
reference) along with the potentiostat instrument allow accurate application of
potential functions and the measurement of the resultant current.
A Three electrode cell used
for anodic stripping
voltammetry.
The working electrode is a
glassy carbon electrode on
which a thin mercury film has
been deposited.
An electrolysis step is used to
deposit lead into the mercury
film as an amalgam.
After the electrolysis step, the
potential is scanned
anodically toward positive
values to oxidize (strip) the
metal from the film.

CYCLIC VOLTAMMETRY
- Involves linear scanning of potential of a stationary
electrode using a triangular waveform
- Solution is unstirred
- The most widely used technique for quantitative analysis
of redox reactions
Provides information on
- the thermodynamics of redox processes
- the kinetics of heterogeneous electron transfer reactions
- the kinetics of coupled reactions

CYCLIC VOLTAMMETRY

- The current resulting from an applied potential is

measured during a potential sweep
- Current-potential plot results and is known as
cyclic voltammogram (CV)

CYCLIC VOLTAMMOGRAM (CV)

Triangular waveform (left) and CV (right) of ferricyanide

Voltammogram
Linear sweep voltammogram for the reduction of a hypothetical species A to give a
product P. The limiting current il is proportional to the analyte concentration and is
used for quantitative analysis. The half-wave potential E1/2 is related to the standard
potential for the half reaction and is often used for qualitative identification of species.

A + ne
iI = kCA

Cyclic Voltammetry
t0 t1 : cathodic wave
Instead of leaving off at the top of the
wave, current decreases at more
negative potential
diffusion is too slow to replenish
analyte near the electrode

t1 t2 : anodic wave
The potential is reversed and, reduced
product near the electrode is oxidized

Epa Epc

2.22 RT 57.0

(mV)
nF
n

(at 25 oC)

Cyclic voltammograms are recorded either with

an osciloscope or with a fast X-Y recorder.
The current decreases after the cathodic peak
because of concentration polarization.
For a reversible reaction, half-wave potential
lies midway between the cathodic and anodic
peaks.

(a) Potential vs time waveform and

(b) cyclic voltammogram for a solution that is
6.0 mM in K3Fe(CN)6 and 1.0M in KNO3.

Fe(C5H5)2

5.375mM (left) and 0.5375 (right) mM Ferrocene in Acetonitrile

Cyclic voltammogram of the insecticide

parathion in 0.5 M pH 5 sodium acetate
buffer in 50% ethanol.

a) Structure of C60 (buckminsterfullerene),

b) Cyclic voltammetry
c) Differential pulse polarography

CYCLIC VOLTAMMETRY
- Assume only O is present initially
- A negative potential sweep results in the reduction of O to R
(starting from a value where no reduction of O initially occurs)
- As potential approaches Eo for the redox process, a cathodic
current is observed until a peak is reached
- The direction of potential sweep is reversed after going
beyond the region where reduction is observed
- This region is at least 90/n mV beyond the peak

CYCLIC VOLTAMMETRY
- R molecules generated and near the electrode surface
are reoxidized to O during the reverse (positive) scan
- Results in an anodic peak current
- The characteristic peak is a result of the formation of a
diffusion layer near the electrode surface
- The forward and reverse currents have the same shape

CYCLIC VOLTAMMETRY
- Increase in peak current corresponds to achievement
of diffusion control
- Decrease in current (beyond the peak) does not depend
on the applied potential but on t-1/2
Characteristic Parameters
- Anodic peak current (ipa)
- Cathodic peak current (ipc)
- Anodic peak potential (Epa)
- Cathodic peak potential (Epc)

CYCLIC VOLTAMMETRY
Reversible Systems
- Peak current for a reversible couple is given by the
Randles-Sevcik equation (at 25 oC)

i p 2.69 x 10 5 n 3/2 ACD1/2 1/2

n = number of electrons
A = electrode area (cm2)
C = concentration (mol/cm3)
D = diffusion coefficient (cm2/s)
= potential scan rate (V/s)

CYCLIC VOLTAMMETRY
Reversible Systems
ip is proportional to C
ip is proportional to 1/2
- Implies electrode reaction is controlled by mass transport
ipa/ipc 1 for simple reversible couple
- For a redox couple
E
o

E pa E pc
2

CYCLIC VOLTAMMETRY
Reversible Systems
- The separation between peak potentials
E p E pa E pc

0.059
V
n

- Used to determine the number of electrons transferred

- For a fast one electron transfer Ep = 59 mV
- Epa and Epc are independent of the scan rate

CYCLIC VOLTAMMETRY
Reversible Systems
- The half peak potential

E p/2

0.028
E 1/2
V
n

- E1/2 is called the polarographic half-wave potential

Multielectron Reversible Systems
- The CV consists of several distinct peaks if the Eo values for
the individual steps are well separated
(reduction of fullerenes)

CYCLIC VOLTAMMETRY
Irreversible Systems
- Systems with sluggish electron transfer
- Individual peaks are reduced in size and are widely separated
- Characterized by shift of the peak potential with scan rate
o

RT
k
n a F
o
Ep E

0.78 ln 1/2 ln
n a F
D
RT

i p 2.99 x 10

1/2

1/2

n n a ACD1/2 1/2

CYCLIC VOLTAMMETRY
Irreversible Systems
= transfer coefficient
na = number of electrons involved in a charge transfer step
ko = standard heterogeneous rate constant (cm/s)
- ip is proportional to C but lower depending on the value of

For = 0.5
ip,reversible/ip,irreversible = 1.27
- That is irreversible peak current is ~ 80% of reversible ip

CYCLIC VOLTAMMETRY
Quasi-reversible Systems
- Current is controlled by both charge transfer and mass transport
- Voltammograms are more drawn out
- Exhibit larger separation in peak potentials compared
to reversible systems
- Shape depends on heterogeneous rate constant and scan rate
- Exhibits irreversible behavior at very fast scan rates

CYCLIC VOLTAMMETRY
Applications
1. Study of Reaction Mechanisms
E = redox step and C = chemical step
E
- Only redox step
O + ne- R

CYCLIC VOLTAMMETRY
Applications
E = redox step and C = chemical step
EC
- Redox step followed by chemical step
O + ne- R + A Z
- R reacts chemically to produce Z
- Z is electroinactive
- Reverse peak is smaller since R is chemically removed
ipa/ipc < 1
- All of R can be converted to Z for very fast chemical reactions

CYCLIC VOLTAMMETRY
Applications
E = redox step and C = chemical step
EC
- Redox step followed by chemical step
O + ne- R + A Z
Examples
- Ligand exchange reactions as in iron porphyrin complexes
- Oxidation of chlorpromazine to produce a radical cation and
subsequent reaction with water to produce sulfoxide

CYCLIC VOLTAMMETRY
Applications
E = redox step and C = chemical step
EC
- Catalytic regeneration of O during a chemical step
O + ne- R + A O
- Peak ratio is unity
Example
- Oxidation of dopamine in the presence of ascorbic acid

CYCLIC VOLTAMMETRY
Applications
E = redox step and C = chemical step
CE
- Slow chemical reaction precedes the electron transfer step
Z O + ne- R
ipa/ipc > 1 (approaches 1 as scan rate decreases)
ipa is affected by the chemical step
ipc is not proportional to 1/2

CYCLIC VOLTAMMETRY
Applications
E = redox step and C = chemical step
ECE
- Chemical step interposed between redox steps
O1 + ne- R1 O2 + ne- R2
- The two redox couples are observed separately
- The system behaves as EE mechanism for very fast
chemical reactions
- Electrochemical oxidation of aniline

CYCLIC VOLTAMMETRY
Applications
2. Study of Adsorption Processes
- For studying the interfacial behavior of electroactive compounds
Symmetric CV
Ep = 0
- Observed for surface-confined nonreacting species
- Ideal Nernstian behavior

CYCLIC VOLTAMMETRY
Applications
Symmetric CV
- Peak current is directly proportional to surface coverage ()
and scan rate ()

n 2 F 2 A
ip
4RT
Holds for relatively
- slow scan rates
- slow electron transfer
- no intermolecular attractions within the adsorbed layer

CYCLIC VOLTAMMETRY
Applications
Symmetric CV
Q (area under peak)

Q nFA

current
Ep,1/2

volts

CYCLIC VOLTAMMETRY
Applications
Symmetric CV
- The surface coverage can be determined from the
area under the peak (Q)
Q = quantity of charge consumed

Q nFA

or

nFA

CYCLIC VOLTAMMETRY

Applications
3. Quantitative Determination
- Based on the measurement of peak current

Additional methods

SPECTROELECTROCHEMISTRY
- Simultaneous measurement of spectral and electrochemical signals
- Coupling of optical and electrochemical methods
- Employs optically transparent electrode (OTE) that allows light to
pass through the surface and adjacent solution
Examples
Indium tin oxide (ITO), platinum, gold, silver, nickel
deposited on optically transparent glass or quartz substrate

SPECTROELECTROCHEMISTRY
-2.5
Epc

Current (Milliamps)

-1.5
ipc

-0.5

0.5

ipa

1.5
Epa

2.5
0.8

0.6

0.4

0.2
Volts vs Ag/AgCl

-0.2

ipa = anodic peak current

ipc = cathodic peak current

-0.4

Modulated Absorbance
Am = -log(I/Io)

SPECTROELECTROCHEMISTRY
Applications
- Useful for elucidation of reaction kinetics and mechanisms
(for probing adsorption and desorption processes)
- Thin layer SE methods for measuring Eo and n (Nernst equation)
- Infrared SE methods for providing structural information
- UV-Vis spectroscopic procedures
- Vibration spectroscopic investigations
- Luminescence reflectance and scattering studies

ELECTROCHEMILUMINESCENCE (ECL)
- Technique for studying electrogenerated radicals that emit light
- Involves electrochemical generation of light-emitting
excited-state species
- Usually carried out in deoxygenated nonaqueous media
Examples of Species
Ru(bpy)32+
Nitro compounds
Polycyclic hydrocarbons
Luminol

SCANNING PROBE MICROSCOPY

- Used to acquire high resolution data of surface properties
- Achieved by sensing the interactions between a probe tip and
the target surface as the tip scans across the surface
Examples
- Scanning Tunneling Microscopy (STM)
- Atomic Force Microscopy (AFM)
- Scanning Electrochemical Microscopy (SECM)

SCANNING TUNNELING MICROSCOPY (STM)

- Direct imaging of surfaces on the atomic scale
- Very sharp atomic tip moves over the sample surface with a
ceramic piezoelectric translator
- The basic operation is the electron tunneling between the
metal tip and the sample surface
- Tunneling current is measured as potential is applied between
the tip and the sample
- Measured current at each point is based on sample-tip separation

ATOMIC FORCE MICROSCOPY (AFM)

- High resolution imaging of the topography of surfaces
(surface structure)
- Allows for nanoscopic surface features while the electrode
is under potential control
- Measures the force between the probe and the sample
- The probe has a sharp tip made from silicon or silicon nitride
attached to a force-sensitive cantilever
- Useful for exploring both insulating and conducting regions

SCANNING ELECTROCHEMICAL
MICROSCOPY (SECM)
- Faradaic currents at a microelectrode tip are measured while the
tip is moved close to the substrate surface immersed in a
solution containing an electroactive species
- The tip currents are a function of the conductivity and chemical
nature of the substrate as well as the tip-substrate distance
Images obtained give information on
- electrochemical activity
- chemical activity
- surface topography

SCANNING ELECTROCHEMICAL
MICROSCOPY (SECM)
- Cannot be used for obtaining atomic resolution
Used to investigate
- Ionic flux through the skin or membranes
- Localized biological activity (biosensors)
- Heterogeneous reaction kinetics

ELECTROCHEMICAL QUARTZ CRYSTAL

MICROBALANCE (EQCM)
- For elucidating interfacial reactions based on simultaneous
measurement of electrochemical parameters and mass
changes at the electrode surface
- Uses a quartz crystal wafer sandwiched between two electrodes
which induces electric field
- The electric field produces a mechanical oscillation in the
bulk of the wafer

ELECTROCHEMICAL QUARTZ CRYSTAL

MICROBALANCE (EQCM)
- The frequency change (f) relates to the mass change (m)
according to the Sauerbrey equation

2mnf o2
A

n = overtone number
fo = base resonant frequency of the crystal (prior to mass change)
A = area (cm2)
= shear modulus of quartz (2.95 x 1011 gcm-1s-1)
= density of quartz (2.65 g/cm3)

ELECTROCHEMICAL QUARTZ CRYSTAL

MICROBALANCE (EQCM)
- Decrease in mass corresponds to increase in frequency
Useful for probing
- processes that occur uniformly across the surface
- deposition or dissolution of surface layers
- ion-exchange reactions at polymer films
- study of polymeric films
- Cannot be used for molecular level characterization of surfaces

IMPEDANCE SPECTROSCOPY
- For probing the features of chemically-modified electrodes
- For understanding electrochemical reactions
- For electron transfer kinetics and diffusional
characteristic studies
Impedance
- Complex resistance encountered when a current flows
through a circuit made of combinations of
resistors, capacitors, or inductors

IMPEDANCE SPECTROSCOPY
- Plots of faradaic impedance spectrum is known as Nyquist plot
Consists of
- a semicircle portion at high frequencies
(corresponds to the electron-transfer-limited process)
and
- a straight line portion at low frequencies
(coreesponds to the diffusion-limited process)

IMPEDANCE SPECTROSCOPY
- The impedance spectrum has only the linear portion
for very fast electron transfer processes
- Very slow electron transfer processes are characterized
by a large semicircle region
- Diameter of the semicircle equals the electron
transfer resistance