CH 3001 Electroanalytical Methods and

Chemical Sensors
Introduction
Voltametry
Potentiometry
Coulometry and Electrogravimetry
Conductimetry
Electrochemical Sensors in brief
Mass transfer
M
+n

mass transport occurs by:
1. diffusion = movement due to
concentration difference
2 migration of charged species
due to potential gradient
3. convection (mechanical
stirring or agitation)
Electrolysis
M
+n

A
-m

(-)
(+)
anode oxidation me A A
cathod reduction M ne M
m
n
+
+

+
Faradic Current (Non-Charging Current)
M
+n

e
(-)
Current due to the transfer of
electron from the electrode to
the ion makes the ion to get
reduced and the current
produced by such processes is
known as Faradic Current. This
current obeys the Faradays
law. This is also known as non-
charging current.
Charging Current (Non-Faradic Current)
+

+

+

+

+

+

+

+

+

+

+

+

+

+

+

+

+

+

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-




M
e
t
a
l

M
+n

Built-up of electrical charge in
the form of a double layer.
Current due to the migration of
ions through the double layer
is known as Charging
Current. This current does not
follow the Faradays law.
Therefore it is known as Non-
Faradic Current.
Voltammetry
Measurement of current as a function of
potential.
Measurement of current under condition of
complete concentration polarization.
A minimal consumption of analyte.
Use of mercury as a electrode in this
method is known as Polarography.
Voltammetry and Polarography
Voltammetry is the electrochemical technique in which
the current at an electrode is monitored as a function
of potential applied to that electrode.
The plot between current and the measured potential
is known as Voltamograme.
In this technique, three-electrode-system is used.
Working Electrode: Where the redox reaction takes
place: usually-> Hg electrode
Reference Electrode: Used to measure the potential
of the working electrode
Auxiliary Electrode: Used to measure the current at
the working electrode
A Modern Polarograph
Principle in Polarograpy
M
+

Charging
Reduction
transfer e arg Ch M ne M
transfer Mass M M
electrode
n
electrod
n
electrode
n
) bulk (
+

+
+ +
Current
Time
e
Faradaic
Cureent
Charging
Current
charged
Three ways of mass transfer when a
potential is applied to the working
electrode:
1. Migration of ions under the influence of the
electric field Migration Current, i
mig

2. Convection current due to the movement of ions
under the influence of hydrodynamic forces
Convection Current, i
con

3. Diffusion of ions from higher to lower
concentration Diffusion Current, i
dif

i
net
= i
mig
+ i
con
+ i
dif

Diffusion rate of the ions o Concentration of the
ions
o diffusion current
o i
net

DC Polarography
Here, the applied potential is DC voltage
The plot between current and the applied
potential is known as a Polarogrph
i
l

E
app

E
1/2

i
Powerful Variations of
Voltametric Methods:
AC Polarography
Normal-Pulse Polarography (NPP)
Differential Pulse Polarography (DPP)
Anodic Stripping Voltammetry (ASV)
Cyclic Voltametry (CV)
Faradic Current (Non-Charging Current)
M
+n

e
(-)
Current due to the transfer of
electrons from the electrode to
the ion makes the ion to get
reduced and the current
produced by such processes is
known as Faradic Current. This
current obeys the Faradays
law. This is also known as Non-
Charging Current.
Charging Current (Non-Faradic Current)
+

+

+

+

+

+

+

+

+

+

+

+

+

+

+

+

+

+

-
-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-




M
e
t
a
l

M
+n

Built-up of electrical charge in
the form of a double layer.
Current due to the migration of
ions through the double layer
is known as charging current.
This current does not follow
the Faradays law. Therefore
known as Non-Faradic
Current.
Polarography Instrument
DC Polarograph
Oxygen Interferences
How to overcome oxygen interference
Bubbling of solution
with pure nitrogen
gas.
Bubbling should be
done before the
commencement of
the analysis.
Through out the
analysis nitrogen
atmosphere is
maintained.
Advantages of DME (compared to
planar electrodes)
clean surface generated
rapid achievement of constant current
during drop growth
remixing of solution when the drop falls
high Hg overvoltage means even metals
with high -ve E
0
can be measured without
H
2
formation

Disadvantages of DME:
Hg easily oxidized, limited use as anode
(E< +0.4 V)
2Hg + 2Cl
-
Hg
2
Cl
2
+ 2e-
nonfaradaic residual currents limit
detection to >10
-5
M
cumbersome to use (toxic mercury)
sometimes produce current maxima for
unclear reasons (use maxima suppressor)

Polarographic Maxima
sometimes
produce
current
maxima
Can be
overcome by
using maxima
suppressor
Powerful improvement of polarography
AC polarogrphy
Normal pulse polarography
Differential pulse polarography
Stripping voltametry
Cyclic voltametry

AC polarogrphy
Instead of DC scan an AC scan is used.
Peaks - the selectivity is higher
Normal pulse polarography
In Normal pulse voltammetry
(polarography) - a potential wave is
applied an HME is used
The sensitivity is higher due to the absence
of charging current
Differential pulse polarography
In Differential pulse voltammetry (polarography) -
a differential potential wave is applied an HME
is used
Both sensitivity and selectivity are higher due to the
absence of charging current and peaks
Differential pulse polarography
pH (Glass Membrane) Electrodes
One of the simpler ion-selective
electrodes (ISE)
Hydrogen Ion imparts a charge across a
hydrated glass membrane
Generally include an internal reference
electrode (Ag/AgCl) and a separate
Ag/AgCl electrode for sensing the charge
imparted by the hydrogen ions
Not as simple to use as you think!
constant pH
External solution
glass
membrane-
hydrated
(50 m thick)
external
reference
electrode
(porous plug)
potential
develops across
membrane due
to pH difference
Combination Glass Electrode
solution level
internal
reference
electrode
Commercial pH meter
3D network of silicate
groups. There are
sufficient cations within
the interstices of this
structure to balance the
negative charge of
silicate groups. Singly
charged cations such as
sodium are mobile in
the lattice and are
responsible for electrical
conductance within the
membrane.
Structure of membrane Glass
Hygroscopicity of Glass membrane
Surface of the glass membrane must be
hydrated to function as a pH electrode.
It can lose pH sensitivity on dehydration, but is
reversible and can be restored by soaking the
electrode in water.
The hydration involves an ion-exchange between
singly charged cations in the glass lattice and
protons from the solution.
+ + + +
+ + Gl H ) solu ( Na Gl Na ) solu ( H
Electrical conduction across
membranes
Conductance within the hydrated glass membrane
involves the movement of Na+ and H+ ions.
Na+ - Charge carriers in the dry interior
H+ - Charge carriers in the gel interface
+ +
+ +
+
+
Gl ) solu ( H Gl H
Gl H Gl ) solu ( H
2
1
The positions of these equilibrium depend on the
H+ concentration on either side and charge on the
glass surface giving potential. The potential
difference between the two sides is known as the
Boundary Potential.
The boundary potential
The potentials associated with each side (solution
1 and solution 2) E
1
and E
2

solution dard tan s is a
a
a
ln
F
RT
E E
) a ln(
F
RT
const E ) a ln(
F
RT
const E
2
2
1
2 1
2 2 1 1
|
|
.
|

\
|
=
+ = + =
The boundary potential depends only upon the
hydrogen ion activity of the external
The asymmetry potential
When glass electrodes two sides are in contact
with identical solutions, we expect zero potential
However a small potential known as the
Asymmetric Potential is encountered.
This gradually changes with time.
Electrode must be calibrated against one or
more standards.
( ) a ln
F
RT
const E E
2 1
| + =
Basic Nernst Equation of a pH Electrode
( ) a ln
F
RT
const E E
2 1
| + =
depends on internal reference
electrode and glass membrane
behavior, which changes with time
Must calibrate with a buffer!
How does the measured voltage, E, vary
with pH?
E
pH
E
Two point calibration
with buffers
E = E 0.0591| pH
Calibration of pH meter
ISFET
A new
pH electrode
What does 0.05916 mean?
It is a constant, if there is a
one-electron reaction
It can be considered as the
equivalent of a constant of
59.16 mV
A pH meter is a high-
impedance potentiometer
(measures voltage)
A pH change of 1 imparts a
change in 59.16 mV to the
potential recorded by the pH
meter!
1 pH unit change= 59.16 mV
mV (relative
readings)
pH
100.00 2.00
159.16 3.00
218.32 4.00
277.48 5.00
336.64 6.00
395.80 7.00
Errors in pH Measurement
1. Uncertainty in your buffer pH due to normal weighing, diluting
errors etc.
2. Junction Potential due to the salt bridge and differences in
Junction Potentials over time due to contamination of the junction
3. Overcome by regular recalibration
4. Sodium Error will result in high concentration of sodium solutions.
The sodium can also impart a charge across the glass membrane.
5. Acid Error (strong acids) can saturate or contaminate the
membrane with hydrogen ions!
6. Equilibration Error is overcome by letting the electrode equilibrate
with the solution
7. Dried out glass membrane (ruins electrode)
8. Temperature. Since temperature affects activities, it is best to have
all solutions at the same, constant temperature!
9. Strong bases. Strongly basic solutions (>pH 12) will dissolve the
glass membrane!
Sodium Electrode
The change in the composition of
the glass membrane permits the
determination of cations other than
H
+
.
By modification of the glass
membrane, you can make an
electrode that is more sensitive to
Na
+
compared to H
3
O
+
.
The modification can be done by
incorporating Al
2
O
3
or B
2
O
3
.
Ion Selective Electrodes
Selectivity Coefficient
Defines how an ISE responds to the species of
interest versus some interfering species
Interferences cause a signal (voltage) to be imparted
on the electrode that is NOT the result of the ion or
chemical species of interest
You want the selectivity coefficient to be as
SMALL as possible
( ) + =
=
)
) , (
) , (
X X A A
X A
A k A
A X
A
X
k
( log
n
0.05916
constant E
analyte the is and ce interferen the is where
to response electrode
to response electrode

|
Examples of Electrodes / Interferences
Solid State Electrodes
Uses a small amount of a doped crystal to transport
charge from the solution to an inner electrode
The inner (sensing) electrode can be a Ag/AgCl electrode,
and a separate Ag/AgCl electrode can be present
Combination electrode
You can use a separate reference electrode also.
Typical equation (Fluoride Electrode):


Use:
Prepare calibration and sample solutions to
similar ionic strengths and temperatures
Connect ISE and reference electrode to
potentiometer (pH meter in mV mode)
Record potentials of calibration solutions
Prepare calibration curve
Measure potential of sample solutions and
calculate fluoride activity!
) ( log x 0.05916 x - constant E
outside - F
A | =
Liquid membrane electrodes
Similar to pH electrode except the
membrane is an organic polymer
saturated with liquid ion exchanger.
Interaction of this exchanger with
target ions resulted in a potential
across the membrane that can be
measured.
Liquid Membrane ISEs
Replace the solid
state crystal with a
liquid ion-
exchanger filled
membrane
Ions impart a
charge across the
membrane
The membrane is
designed to be
SELECTIVE for the
ion of interest
Liquid membrane electrodes
The reservoir forces exchanger into
membrane.
The exchanger forms complexes with species
of interest.
This results in a concentration difference and
the resulting potential difference can be
measured.
Gas Sensing Electrodes
Still considered ion-
selective
Works by the
permeation of gas
across a selective
membrane
Also called compound
electrodes
The gas changes the
pH inside the
electrode (on the
inside of the
membrane) and this
signal is proportional
to the gas
concentration.
Gas Sensing Electrodes
Enzyme Electrodes
Enzyme Electrodes
Enzyme Electrodes
EE transducer
Analyte signal recognition
Enzyme Electrodes
EE transducer
Analyte No signal No recognition
Potentiometric Titrations
E
Cell
V
Titrant
End Point
Potentiometric Titration
How does the pH change during an acid-
base neutralization reaction?

Measure pH as the titrant is added.

pH
Volume of titrant (mL NaOH)
HCl + NaOH NaCl + H
2
O
pH = 7
Equivalence point pH
How do we locate the equivalence point?
pH
Volume of titrant (mL NaOH)
HCl + NaOH NaCl + H
2
O
pH = 7

Just acid


Just salt


Both acid & salt


xs NaOH & salt

What is present at various points?
pH
Volume of titrant (mL NaOH)
HCl + NaOH NaCl + H
2
O
The slope between each pair of data points.
How is the slope changing?
increasing slope
decreasing slope
7
inflection point - changed
from increasing to decreasing
Using the derivative to
locate the equivalence point
0
2
4
6
8
10
12
14
16
0 5 10 15 20
volume of NaOH
p
H
0
5
10
15
20
25
30
35
40
45
50
d
e
r
i
v
a
t
i
v
e
pK
a
The maximum of the derivative locates the equivalence point.
Electrogravimetry & coulometry
Both are electrolysis processes
Constant potential electrolysis potential of the
working electrode is held constant
Constant current electrolysis current at the
working electrode is held constant
Complete electrolysis
Amount of material discharge Electrogravimetry
Amount of electricity required - Coulometry
Electrogravimetry
Mostly used in metal ion analysis
Deposits on cathode as the metal
Weight of the cathode before and after the
complete electrolysis
Electrodes used in the electrolysis must be
inactive

Decomposition potential
Increase of the potential at the working
electrode leads to give a current at a certain
potential.
Current
potential
Decomposition potential
Factors effecting decomposition potential
Equilibrium potential
Ohmic potential
Overpotential
activation and
concentration
cop aop op eq d
E E E E E + + + A =
Selectivity in electrolysis
Current
potential
E
1
E
1

Applied potential between E
1
and E
2
only one metal ion
gets reduced.
The electrolysis under constant potential is
selective.
The electrolysis under constant current is
non-selective.

Selectivity in electrolysis cont...
Apparatus for electrogravimetry
Depolarization of electrodes
As the current decreases, the potential
needs to be increased in order to offset IR
drop and then excess ions present in the
solution may start to discharge. Under
these circumstance, the electrode is said
to be depolarized. This will lead to co-
deposit and can start before the ion
interested to complete the deposition. This
will lead to interferences.
Interferences in Electrolysis
Example:
Mixture of Cu(II) and Pb(II)
Deposition of Cu(II) starts
at 0.2 V. Due to the IR drop,
in order to keep the current
constant,potential should be
increased.
In acidic solutions reduction
of H
+
occurs and deposition
may not adhere to the
electrode.
Depolarizers in electrolysis
In order to avoid H
2
evolution from cathode,
we add nitrate ions into the solution.

O H 3 NH e 8 H 10 NO
H
2
1
e H of Instead
2 4 3
2
+ + +
+
+ +
+
Here, the nitrate ion is called depolarizer
which avoids the reduction of H
+
.
Electrolysis under constant current
This is lack of selectivity and do not have
any practical importance when a mixture
of ions are present in the solution.
However, if a single ion is present, this
method is more advantages since the time
necessary for complete electrolysis can be
controlled.
Electrolysis under constant potential
The potential of the working electrode can
be controlled and kept at a constant value.
However as the electrolysis is going on the
current is continuously dropping (the rate
of discharge is dropping).
It takes a longer time for complete
electrolysis, but however interferences can
be avoided.
Mixture of Cu(II) and Pb(II)
The deposition potential for Cu(II) 0.2 V
The deposition potential for Pb(II) - -0.15 V
By controlling the potential, Cu can be
deposited first and then Pb can be
determined by taking the weight of the
cathode at each occasion.

Electrolysis under constant potential
The quantity of electrical charge
Under constant current Q = it


Under constant potential


By measuring the amount of electricity one can
calculate the amount of material discharge.
}
=
t
o
idt Q
Coulometry
Two types of methods
Constant potential coulometry - selective
Constant current coulometry- non-selective
Coulometry is same as electrogravimetry but
instead of measuring the weight of discharge
material, here, the amount of electricity is
measured which can be related to the amount of
material according to Faradays law.
Coulometric Titration
Here the titrant is electrically generated.
Example: Analysis of As(III)
The solution containing As(III) was added
to excess I
-
and electrolysis carried out.
The I
2
produced will react with As(III)

+
+
I 2 e 2 I
e 2 ) V ( As ) III ( As
2