X.

Yao
CHEM 3334

Potentiometry, Voltammetry, and

Amperometry
— Methods make use of electrochemical
cells to perform measurements
Goal: To determine concentrations through redox reactions
How: By setting up appropriate electrochemical cells

Ecell = Eprobe = Eindicator- Ereference

Quantitative analytical methods that are based on electrochemical

properties of a solution of analyte when it is made part of an
electrochemical cell.
Three Common Interfacial Electrochemical
Techniques X. Yao
CHEM 3334

Interfacial Electrochemical Techniques

Static
Dynamic Techniques
Techniques
(i ≠ 0)
(i = 0)
Potentiometry Controlled Potential
(Measuring E) (Measuring i)

Viable Potential Fixed Potential

Galvanic Cell
Redox Chemical Reaction
To Energy (Potential)
Voltammetry Amperometry

Electrolytic Cell
Energy Input/Stimulus (Potential)
To Redox Chemical Reaction
To Electron Flow (Current)
 Interfacial
Electrochemical X. Yao
CHEM 3334

Techniques

Galvanic cell
Voltammetry
measure i

Electrolytic cell

Electrolytic cell (Reference chart not to be

quizzed on)

Analytical Chemistry 2.0 (Harvey)

 Three Common Interfacial Electrochemical Techniques X. Yao
CHEM 3334

• Potentiometry
– Measurement of a potential (voltage) at an electrode (relative to a
reference in the absence of current flow)
• Equil. Voltage is measured (Eeq)
– Most common (pH, pIon, …)

• Voltammetry
– Measurement of current as a function of applied potential that is
modulated. Usually involves three electrodes (working, counter and
reference)

• Amperometry
– Measurement of a limiting current at a constant potential, developed
between two electrodes. The current is related to the mass transfer,
voltage, temperature and concentration …
– Common as detectors in LC with very low detection limits
 Five Important Concepts in X. Yao
CHEM 3334

Electrochemistry
1. The electrode’s potential determines the analyte’s form
at the electrode’s surface.
2. The concentration of analyte at the electrode’s surface
may not be the same as its concentration in bulk
solution.
3. In addition to an oxidation–reduction reaction, the
analyte may participate in other reactions.
4. Current is a measure of the rate of the analyte’s
oxidation or reduction.
5. Current and potential cannot be simultaneously control.

Analytical Chemistry 2.0 (Harvey)

 A redox reaction happens on the
surface of an electrode X. Yao
CHEM 3334

LOW concentration of electrons

1. The Electrode’s
Potential Determines the
Analyte’s Form
--Be Happy!
Fe2+

HIGH concentration of electrons

Fe3+

Note: redox reactions take place at the surface of electrodes

Analytical Chemistry 2.0 (Harvey)
 2. Interfacial Concentrations May Not Equal X. Yao

Bulk Concentrations CHEM 3334

Reminder: The Nernst Equation for a

reversible process:

E = Eo – (2.303RT/nF) Log (ared/aox)

The Nernst equation for Fe3+ and Fe2+ a (activity), related directly to
concentration

Bulk
Solution

Diffusion Bulk
Layer Solution

Analytical Chemistry 2.0 (Harvey)

3. The Analyte May Participate in Other Reactions and
Physical Processes X. Yao
CHEM 3334
— Possible steps in electron transfer processes
• Charge-transfer may be rate limiting
• Nernst equation

Rate limiting step may be mass transfer

Rate limiting step may be chemical reaction

Analytical Chemistry 2.0 (Harvey)
Adsorption, desorption or crystallization polarization
 4. Current is a measure of rate X. Yao
CHEM 3334

• The reduction of Fe3+ to Fe2+ consumes an electron, which is drawn

from the electrode. The oxidation of another species, perhaps the
solvent, at a second electrode serves as the source of this electron.
The flow of electrons between the electrodes provides a measurable
current (indicated with I or i).

• Because the reduction of Fe3+ to Fe2+ consumes one electron, the

flow of electrons between the electrodes—in other words, the
current—is a measure of the rate of the reduction reaction.

• One important consequence of this observation is that the current is

zero when the reaction Fe3+ ⇋ Fe2+ + e− is at equilibrium.

Analytical Chemistry 2.0 (Harvey)

 5. Current and potential cannot be
X. Yao
simultaneously controlled CHEM 3334

• If a solution of Fe3+ and Fe2+ is at equilibrium, the current is zero and

the potential is given by the Nernst equation.

• If the potential is changed away from its equilibrium position, current

flows as the system moves toward its new equilibrium position.
Although the initial current is quite large, it decreases over time
reaching zero when the reaction reaches equilibrium. The current,
therefore, changes in response to the applied potential.

• Alternatively, we can pass a fixed current through the

electrochemical cell, forcing the reduction of Fe3+ to Fe2+. Because
the concentrations of Fe3+ and Fe2+ are constantly changing, the
potential, as given by the Nernst equation, also changes over time.

• In short, if we choose to control the potential, then we must accept

(measure) the resulting current, and we must accept (measure) the
resulting potential if we choose to control the current. Analytical Chemistry 2.0 (Harvey)
 X. Yao
CHEM 3334

Galvanic vs Electrolytic
Cells
Properties of Galvanic and Electrolytic Cells
Galvanic Cell Electrolytic cell
A Galvanic cell An electrolytic cell
converts chemical energy into electrical energy. converts electrical energy into chemical energy.
The redox reaction is spontaneous The redox reaction is not spontaneous
and thus produces electrical energy. and thus requires input of electrical energy to initiate the
reaction.
The two half-cells are set up in different containers, Both the electrodes are placed in the same container
being connected through the salt bridge or porous in the solution of molten or dissolved electrolyte.
partition.
The anode is the negative electrode The anode is the positive electrode
and cathode is the positive electrode. and cathode is the negative electrode.
The reaction at the anode is oxidation and that at the The reaction at the anode is oxidation and that at the
cathode is reduction. cathode is reduction.
The electrons are generated by the species getting The external battery supplies the electrons.
oxidized. The supplied electrons enter the cathode, resulting
The generated electrons generated move from anode to reduction on the electrode surface,
the cathode in the external circuit. and removed from the anode, resulting oxidation.
http://chem.libretexts.org/Core/Analytical_Chemistry/Electrochemistry/Electrolytic_Cells
 Typical Uses X. Yao
CHEM 3334

• Study redox chemistry

– electron transfer reactions, oxidation,
reduction, organics & inorganics, proteins
– O + ne- = R
– 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)
 X. Yao
CHEM 3334

Potentiometry

• pH and Ion Selective Electrodes

• Potentiometric Sensors

• When i is controlled at ~0 Amps,

Eeq is measured

• In general, at 25 oC
Eeq = const – 0.0592 log aX
 Relationship between cell potential and conc.
X. Yao
a) one e transfer per electrode
- CHEM 3334

b) electrodes have ext. connections

c) salt bridge allows flow of charges
Zn(s) + Cu2+  Zn2+ + Cu(s)
voltmeter
Ecell = Ecathode – Eanode- IR
e- IR  boundary potentials
Zn Cu
- +
Cl KCl K

 oxidation  reduction
 produces e-
l l  consumes e-
ce
 anode ZnSO4 0.0100 M CuSO4 0.0100 M  cathode
C se nt
D p re
re de!
Zn(s)  Zn2+ + 2e- Cu2+ + 2e-  Cu(s) s t
u ctro
m
on e e el e
it her erenc
E ref
the
Note: Semi-cell reactions always written as reductions.
We always talk about semi-cell reduction potentials Zn2+ + 2e-  Zn(s)
 X. Yao
CHEM 3334

Measurements in Potentiometry; i = 0 Amps; equilibrium

Cell (probe): working electrode (WE) + reference electrode (E half cell = constant)

Working or Indicator
Electrode

Ecell = Eprobe = EWE – Eref - Ejunction

Reference electrodes: critical to both potentiometry and voltammetry
They keep a nearly constant half cell potential during experiment. X. Yao
CHEM 3334

Reference Electrode 1:
Normal Hydrogen Electrode (NHE): Pt| H2 (1 atm), HCL (0.01 M)E ||
SET THE STANDARD, E = 0.00 V, but not practical

Indicator Electrode

Also called as the Standard Hydrogen Electrode (SHE)

2 H+(aq, 1M) + 2 e-  H2 (1atm) E° = 0.00 V
Reference Electrode 2:
Saturated Calomel Electrode (SCE): Hg| Hg2Cl2 (s), KCl (sat’d) X. Yao
CHEM 3334

Set up as self-contained half cell

Half cell potential of the SCE –

serves as a reference against which
other electrodes are measured (any
experiment; e.g., potentiometry or
voltammetry).

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

Use Nernst equation:

E = Eo - [RT/nF] ln (aCl2 aHg2/acalomel);
but a of pure solids =1

only aCl- remains in the log term, and

E = Eo’ - [0.0592/2] log [Cl-]2 or
E = Eo’ - 0.0592 log [Cl-]; sat’d KCl is
~3.5 M at 25 oC
Contact to test solution
So ESCE = 0.2415 V vs. NHE at 25 oC
Reference Electrode 3:
Ag|AgCl (s), KCl (sat’d.) X. Yao
CHEM 3334

EAg/AgCl = 0.199 V vs. NHE at 25 oC

AgCl(s)+e– ⇌ Ag (s)+ Cl– (aq)

Converting Potentials Between X. Yao
CHEM 3334

Reference Electrodes
 X. Yao
CHEM 3334

Working Electrodes

Ion Selective Electrodes

Ion Selective Electrodes (ISE) - Electrodes based on membrane
potentials are called ion-selective electrodes. Surface usually is a X. Yao
CHEM 3334
membrane that adsorbs the ions, Eeq measured at I = 0 Amps.

In pH electrode, the membrane is a thin glass layer

0.1 M HCl

Stand alone glass pH electrode Glass pH electrode combined

must be used with reference with internal reference electrode
 X. Yao
CHEM 3334

Figure 18.4 The pH membrane electrode. In the absence of H+, the inner and
outer surfaces (dark blue) are composed of sodium silicate. In the presence of H+,
some of the Na+ within the surface layer of the glass is replaced by H+. In (A) both
internal and external solutions are neutral, with equivalent displacement of Na+ by H+,
and in (B) there is an acidic external solution, with excess displacement of Na+ by H+
(more H+ in the glass membrane surface layer, after having displaced sodium ions).

Instrumental Analysis Granger, Yochum, Granger, and Sienerth Copyright ©

2017 Oxford University Press
 How a glass pH electrode responds to H+ ions X. Yao
CHEM 3334
(must store in in water or buffer to maintain hydrated layer)
H+ DOES NOT cross the membrane

Ag/AgCl Inner hydrated Dry glass outer hydrated Test solution

0.1 M HCl layer layer aH+ , soln
aH+ = const
a2 a1
0.1 mm 50 mm
E2 E1
EM = E1 – E2 + Eint ref; EB = E1 – E2 (boundary E)

Ecell = const + EB
EB is related to a1 and a2, but a2 is constant (0.1 M HCl)
These ion activities control the membrane potentials,
E1 and E2, and so control EB, at 25 oC

EB = E1 – E2 = 0.0592 log (a1/a2)

 Ion Selective Electrodes (ISE) obey Nernst-like equations
X. Yao
CHEM 3334
E = const + [0.0592/z] log aion ISE measure activity, not conc.

If the ion is H+, EB = E1 – E2 = 0.0592 log (a1/a2) (EB is related to a1 and a2,
but a2 is constant (0.1 M HCl). These ion activities control the membrane
potentials, E1 and E2, and so control EB, at 25 oC)

E = const - 0.0592 pH; pH = -log aH+ (activity of a1)

Problem 23-1: What is meant by Nernstian behavior of an indicator electrode

Nernstian region, slope = 0.0591/z
(E = const + [0.0592/z] log aion)
E, mV

Most pH meters read pH directly,

But must be calibrated daily
Log aion pH = -log aH+
Fast response is important, <1 s in buffer for most pH electrodes
Problem 23-2. What are sources of the acid and alkaline errors in X. Yao

pH measurement with a glass electrode? CHEM 3334

Alkaline errors arise from the exchange of singly charged ions, such as
sodium or potassium ions, in the surface of the glass membrane with the
protons from the water. The potential then responds to the alkali metal ion
activity as well as to the hydrogen ion activity.
In basic solutions or high salt conc. NaCl, KCl,
Na+ and K+ interfere by adsorbing to the glass membrane
then pHobs < true pH (i.e., 0.1 M NaOH, pH 13, [Na+] is 0.1 M, [H+]= 1 x 10-13. Large error
due to high [Na+], low [H+])

In general, the Nicolsky equation can be used for ISEs:

Ecell = const + 0.0592 log [a1 + Σ Kjaj], j = 1….n interfering ions

Kj = selectivity coefficient

Acid error (pH < 1). Not all causes of the acid error in pH measurmenets with
a glass electrode are well understood. One erroe source is thought to arise
from a satutaion effect in which all the surface sites on the glass are
occupied by H+ ions.

pH electrodes reliable between pH 1 and 13 only

 ISE’s for ions other than H + X. Yao
CHEM 3334

• glass membranes, Na+, K+, NH4+ —different

composition than pH
• solid state membranes, F-, S-
• liquid membranes, Ca+
• gas sensitive electrodes CO2, H2S, NH3
• enzyme electrodes – biological molecules
• Can all be used with pH meter in mV-mode
 Glucose Sensor
X. Yao

glucose + O2  H2O2 + gluconic acid CHEM 3334

O2 + H2O + 2e-  H2O2 + OH-

glucose
oxidase

Modified Clark cell for the indirect detection of

glucose by monitoring decreased oxygen levels.
Scheme for the glucose
oxidase catalyzed oxidation
of glucose, resulting in the
reduction of O2 to H2O2.
Voltammetry is a dynamic method X. Yao
CHEM 3334

 Vary Eapplied and measure Faradaic current

 Current related to rate of reaction at an electrode

O + ne- = R, Eo in Volts

I = kA[O]
 I: Faradaic current, caused by electron transfer
 [O]: analyte concentration
 A = probe area
 k = const

 Also, a non-faradaic current flows as part of

the background current
 Analytical Electrolytic Cells
X. Yao
CHEM 3334

• Use external potential (voltage) to drive

reaction
• Eapp 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
 Voltammetry and X. Yao
CHEM 3334

Amperometry
Involves oxidations and reductions at electrode,
Electron transfer (ET) across electrode-solution interface
Amperometry: constant voltage applied
Voltammetry: voltage scanned
Current is measured in both methods
I = kC

We will cover 4 kinds, quiet solution, hydrodynamic,

cyclic, and pulsed
 Analytical Applications of Electrolytic Cells
X. Yao
CHEM 3334

• 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 respect to bulk solution
• Mass transport brings unreacted species to electrode surface
 Typical 3-electrode X. Yao
CHEM 3334
Voltammetry cell

Reference electrode
Counter
electrode

Working electrode
(only planar tip active)

O Reduction at electrode
O Causes current flow in
e- Mass transport External circuit

R R

End of Working electrode Bulk solution

insulation Reduction at electrode causes current
flow in external circuit
X. Yao
O O CHEM 3334

e- Mass transport

R R

Working electrode

O + ne = R, Eo in Volts, at E < Eo;

E more negative-reductions
E more positive-oxidations
Important processes:
1. Mass transport of O to electrode
2. Electron transfer (ET) across electrode-solution interface
3. Mass transport of R away from electrode
 Voltammetry (measures I vs. E)
When I is not zero, there is an IR drop in potential Need of wire
Potentiostat for decoupled measurement of E and I X. Yao
CHEM 3334

potentiostat
insulator electrode
material
E i
reference working electrode
N2 counter
inlet Output, I vs. E, quiet solution

Electrochemical cell reduction

Input: E-t waveform

E, V

time

Hydrodynamic – electrode rotates

Or is in a flow stream
Alternative: Quiet solution
 Potential drop across cell resistance
X. Yao
CHEM 3334

Figure 19.8 Depiction of the IR drop in a three-electrode cell. R1 is the

solution resistance, and R2 is the resistance imparted by the porous barrier
between the working and counter electrodes. The total IR drop is the sum of the
voltages lost over both resistances.
Instrumental Analysis Granger, Yochum, Granger, and Sienerth Copyright ©
2017 Oxford University Press
 Electrolysis: Faradaic and Non-Faradaic
Currents X. Yao
CHEM 3334

• Two processes at electrode/solution interface

produce current when Eapp<< Eo (for reductions)
– Direct transfer of electrons, reduction (or oxidation)
• 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; no
reduction of oxidation

• 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
–
 X. Yao
CHEM 3334

• 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, at soln. interface
– NOT in bulk solution
 NERNST Equation: Fundamental
Equation for reversible electron transfer at X. Yao
CHEM 3334

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) ; a = activity

aR = fRCR 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.
Ionic strength I = Σ zi2mi, X. Yao
CHEM 3334

Z = charge on ion, m = concentration of ion

Debye Huckel theory says log fR = 0.5 zi2 I1/2

So fR/fO depends on I, it is 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

 The three common
X. Yao
shapes for voltammograms CHEM 3334

Input: E-t waveform

Output, I vs. E, stirred solution
(hydrodynamic voltammetry)

E, V

Output, I vs. E, quiet solution

time

Different shapes caused

by different mass
transport
 Mass Transport X. Yao
CHEM 3334
• Diffusion: the last step of mass transport of analyte to
electrode surface
– due to conc. Gradient, in quiet solutions region near electrode
gets depleted by O + ne = R

O
In bulk solution
e -
Mass transport [O] remains constant

R R

X = distance from electrode

JO = rate of diffusion (flux) = - D dCo/dx|x=o Fick’s First Law

D = diffusion coefficient, cm2/s; dCo/dx|x=o = concentration gradient

I = -nFA JO so I = nFA D dCo/dx|x=o

Other types of mass transport X. Yao
CHEM 3334

• Migration: source of charging current and control

– movement of ions in electric field, suppressed by adding large
conc. of inert electrolyte, e.g., 0.1 M KCl, or 0.1 M NaCl
– At Csalt > 20 X CO, electrolyte ions migrate, migration of O is
negligible
– In most voltammetry experiments, 0.1 M or more of an inert salt
is added

• Convection: determining the shape of current

– stirring or flowing solution past electrode, basis of hydrodynamic
voltammetry
– Rate of mass transport is constant and gives rise to the steady
state or limiting current
 Mass Transport
X. Yao
CHEM 3334

Diffusion
B e Tested
Eq. 19.2 ar ning, Not
anc ed Le
Enh

Migration
Eq. 19.3

Convection
Eq. 19.4

Instrumental Analysis Granger, Yochum, Granger, and Sienerth Copyright ©

2017 Oxford University Press
 Why are voltammetry shapes different?
X. Yao
CHEM 3334

t increase
t1
Independent
of time
t2

t3

Quiet solution voltammetry, diffusion Hydrodynamic voltammetry, convection

Controlled, CO at electrode decreases controlled, CO at electrode is constant
with time, so a peak is observed as scan with time, so limiting current is observed
proceeds, at longer times
 X. Yao
CHEM 3334

e Tested
Not B
d Learning,
ce
Enhan
 Electrical Double layer at Electrode
X. Yao
CHEM 3334

B e Tested
ar ning, Not
hanc ed Le
En

• Heterogeneous system: electrode/solution

interface
• The Electrical Double Layer, e’s 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.
 e Tested X. Yao

, Not B
CHEM 3334
r ning
anc ed Lea
Enh
 X. Yao
CHEM 3334
Linear Sweep voltammetry, quiet solution,
diffusion control Rotating disk voltammetry
convection control
 X. Yao
CHEM 3334
Potential step; chrono-amperometry X. Yao
CHEM 3334

Eo’ O + ne = R
Plotting Conventions for Voltammetry X. Yao
CHEM 3334

Classic in US IUPAC

anodi
oxidizing

c
cathodic
reducing

negative positive
 Cyclic Voltammetry
Input waveform X. Yao
CHEM 3334

Scan rate
0.001 to 1 Million V/s
Usually to 100 V/s

OR
Output, reversible O + ne = R

Ipc/ipa = 1, |Epc-Epa| = 59/n mV at 25 oC

RO Eo’ is midpoint between Epc and Epa

DEpc/Dn = 0; for a reversible, fast ET

Above, c=cathodic, a = anodic, p=peak
Effect of charging current on high scan rate CV X. Yao

e Tested CHEM 3334

r ning, Not B
anc ed Lea
Enh

Figure 19.20 Comparison of the blank and solute CVs at scan rates of 10 mV/s
and 150 V/s. At 10 mV/s (A), the charging current seen in the blank is significantly
smaller than the analyte scan. However, at a scan rate of 150 mV/s (B), the charging
current is the dominant source of current. The analyte signal is barely discernible
above the “background” current.

Instrumental Analysis Granger, Yochum, Granger, and Sienerth Copyright ©

2017 Oxford University Press
 High speed CV at UME
B e Tested X. Yao
CHEM 3334

r ning, Not
anc ed Lea
Enh

Figure 19.22 CVs obtained from a 10 mM anthracene solution at a UME at

scan rates of (A) 22 kV/s, (B) 56 kV/s, (C) 320 kV/s, and (D) 1.7MV/s. The
working electrode was a 5 µm gold disk electrode.
Instrumental Analysis Granger, Yochum, Granger, and Sienerth Copyright ©
2017 Oxford University Press
 Electrochemical Window
X. Yao
CHEM 3334

Figure 19.16 CV of Pd(bpca)2 in acetonitrile exhibiting the

potential limits imposed by the electrochemical window of the solvent
with 0.1 M TBAPF6 added as the SE.

Instrumental Analysis Granger, Yochum, Granger, and Sienerth Copyright ©

2017 Oxford University Press
 Electrochemical Window
X. Yao
CHEM 3334

Instrumental Analysis Granger, Yochum, Granger, and Sienerth Copyright ©

2017 Oxford University Press
 Reversible Diffusion controlled CVs
Randles-Sevcik Equation X. Yao
CHEM 3334

n = # o f e-’s
V = n, scan rate

Ipc Ipc

~5 mM
n1/2 Co
Detection limit ~5 mM/n
Reproducibility ±2%
 Current types and measurement X. Yao
CHEM 3334

• Charging current
– source

• Residual current
– Charging current
– Faradic current of impurities

• Faradic current of target analyte

– What matters
 Charging Current
X. Yao
CHEM 3334

Figure 19.6 Schematic diagram of the electrode surface

before and after the application of a potential to the electrode.

Instrumental Analysis Granger, Yochum, Granger, and Sienerth Copyright ©

2017 Oxford University Press
Potential-excitation X. Yao
normal pulse polarography
signals and CHEM 3334

voltammograms
for (a) normal pulse polarography,
(b) differential pulse polarography,
(c) staircase polarography, and (d) differential pulse polarography
square-wave polarography.
The current is sampled at the time
intervals shown by the black
rectangles.

staircase polarography

square-wave polarography
 Normal Pulse Voltammetry – Invented by Sir G. Barker in 1960s
Digital rather than analog method; all instruments now digital X. Yao
CHEM 3334

Ilim

Method discriminates against non-Faradaic current since measurements

made when the non-Faradaic current is very small, end of pulse (60 ms)

Ilim = nFACoDo1/2/π1/2tp1/2; 10-fold more sensitive than CV

 Square Wave Voltammetry X. Yao
CHEM 3334

net

forward

reverse

o rize
Detection limit 10-9 M/n mem
Net current otto
n n
qu atio Current function
The most sensitive voltammetric method, detection limit ~10 M/n
-9 E
Other advantages: symmetric peak shape, better resolution than CV, discriminates
the best against non-Faradaic current (low background)
 Solid working electrode
X. Yao
CHEM 3334

B e Tested
r ning, Not
anc ed Lea
Enh

Figure 19.19 Schematic diagram depicting typical construction of

disk electrodes made using metal wire and glassy carbon rod or metal
disk.

Instrumental Analysis Granger, Yochum, Granger, and Sienerth Copyright ©

2017 Oxford University Press
 Working Electrodes
X. Yao
CHEM 3334

Instrumental Analysis Granger, Yochum, Granger, and Sienerth Copyright ©

2017 Oxford University Press
 B e Tested X. Yao

g, Not
CHEM 3334
ar nin
hanc ed Le
En

Instrumental Analysis Granger, Yochum, Granger, and Sienerth Copyright ©

2017 Oxford University Press
 Diffusion at Ultramicroelectrodes (UMEs) X. Yao
CHEM 3334

B e Tested
r ning, Not
anc ed Lea
Enh

Figure 19.21 Comparison of planar diffusion at a millimeter-

scale electrode (A) and nonplanar (spherical) diffusion at a UME
(B).

Instrumental Analysis Granger, Yochum, Granger, and Sienerth Copyright ©

2017 Oxford University Press
 Nanoscale array electrode
X. Yao

B e Tested CHEM 3334

r n ing, Not
hanc ed Lea
En

Figure 19.24 An example of an ultramicroarray electrode. The full

array (A) has more than 5 million UMEs (100 nm diameter each) in a 1 mm2
grid. A close-up view of the electrodes is seen in (B).

Instrumental Analysis Granger, Yochum, Granger, and Sienerth Copyright ©

2017 Oxford University Press
 X. Yao
CHEM 3334

How are electrodes engineered?

Ag + Cl-  AgCl(s) + e-
O2 + 4H+ + 4e-  H2O

Liquid membrane
electrode sensitive to Clark voltammetric oxygen sensor
M2+

B e Tested
r ning, Not
hanc ed Lea
En
 X. Yao
CHEM 3334

How are electrodes engineered?

microring microdisk lithograpically- microband

microdisk array made
microband array

microsphere
single fiber fiber
Micro array
hemispher
e
REDOX reaction
that produces Eind

Tested Electrode with

B e
r ning, Not immobilized
anc ed Lea antibodies
Enh
ELISA-type with hydroquinone
phosphate/diphosphate reaction