Review:

Potentiometric methods measure the potentials at

electrodes by a suitable coupling of a reference
electrode; as a potential difference E (Ecell).

Electro-analytical Techniques At the electrode the redox reaction has

reached equilibrium. Under such a situation there
is no net transfer of charge (current) across the
Dynamic electrode interface.

Thus as the measurement is made very little or no

current is drawn by the measuring device
(potentiometer).

Example (electrode):

Pt/Sn+2(aSn+2+,), Sn+4(aSn+4+) Eel

Sn+4 + 2e = Sn+2
Electrochemistry in Stirred Solutions
The concentrations at the
electrode surface are nearly
the same as that in the
bulk solution.

Disturbing the equilibrium (reduction here):

Metal electrodes are generally polarizable.
Pt/Sn+2(aSn+2+,), Sn+4(aSn+4+) E <Eel (E sufficiently
negative) To make them non-polarized, stir the solution so that
the concentration at the surface is the same as in the
Sn+4 + 2e → Sn+2 bulk.

The concentrations at the Reference electrodes are generally non polarizable.

electrode surface are
different from that in the
bulk solution – polarization.

Working electrode
Electrode at which reaction of
interest occur.
Application of a potential sufficiently different from the
equilibrium potential would drive the half reaction
in one direction. This would lead to a flow of charge
(electrons) i.e. a current, i.

Current, I. amp
dq
i=
dt t

And quantity of charge q = it; t = time if i is held constant; q = ∫ idt

t 0
More precisely; q = ∫ idt t
0
q ∫ idt
Moles of material involved; =0
nF nF

power source
However, potential at a single electrode cannot The spontaneous
be changed, two electrodes are required. reaction; propensity measured by Ecell;

The second electrode –

Auxiliary (or counter) electrode.

A redox reaction would occur at the counter

electrode simultaneously.
Cu = Cu+2 + 2e
½ O2 + 2H+ + 2e = H2O

power source Note: electrolysis is not an equilibrium situation.

Electro-deposition of Copper.
Non-spontaneous process.
The energy required to
effect the reaction
is drawn from the
external power source.
1. Redox reaction occur at the electrode interfaces,
interchange of electrons occur. The reaction is
‘forced’, it is a energetically uphill process.
Vapp
i
2. Oxidation reaction occur at the anode,
interchange of electrons occur. The reaction is
‘forced’, it is a energetically uphill process.

3. Reduction reaction occur at the cathode,

Cu+2 + 2e → Cu interchange of electrons occur. The reaction is
H2O →½ O2 + 2H+ + 2e ‘forced’, it is a energetically uphill process
 a. Reduction; Cu+2 + 2e → Cu
Overcoming activation energy requires input of
energy.
Achieved by increasing the negativity of the
cathode. Eapp,cathode < Eeq.cathode
Minimal applied potential (difference) required
to effect Electrolysis.
Cu Cu

Cu+2+2e

Cu+2+2e

b. Oxidation; H2O →½ O2 + 2H+ + 2e

To overcome the activation energy required an
input of energy, increasing the positivity of the
anode.
Eapp,anode > Eeq.anode

½ O2 + 2H+ + 2e

½ O2 + 2H+ + 2e

H2 O H2 O

Vapp= Eapp,anode – Eapp,cathode > Ecell Eapp = Ecathode – Eanode + overpotentials + iR

Vapp – Ecell = Cell overvoltage

In addition the to drive a current the resistance
of the cell must be overcome as well; IR drop,
Ohmic potential.

Vapp = Ecathode – Eanode + overpotentials + iR

Further, the depletion of material at the electrodes

would require the movement of material from the
bulk of the solution (diffusion – if solution unstirred)
and that involves some energy as well -
Concentration overpotential.
 Three electrode cell

How the applied potential difference distributes itself

between the two electrodes is harder to decipher.

Often it is necessary to find the actual potential

on the working electrode –

technique – three electrode cell.

Controlled potential analysis

Electrogravimetric Analysis

This method employs an

electric current to deposit
a solid on an electrode
from a solution.
working Two or three electrode circuit
electrode used, either a constant current
or a constant potential is
applied to the pre-weighed
working electrode
 Coulometry:

Coulometry determines the unknown concentration

of an analyte in solution by completely converting the
analyte from one oxidation state to another.

Coulometry is an absolute measurement similar to

gravimetry or titrimetry and requires no chemical
mass deposited standards or calibration.
= moles
Molar mass
Useful for determining absolute concentration
of standards.

Coulometry
Coulometry
Constant current mode
dq q=i t
i=
dt Coulombs of
t charge measured
q ∫ idt
=0
nF nF

Coulometric determination with amperometric detection.

Coulometry: Determine
Br
+ Br2 →
Br

Reagent electrolytically generated,

q for reagent generation measured.

Br- → Br2 +2e

it
moles _ Br2 =
2F
Amperometry: Constant potential mode
In amperometric experiments the potential of the
indicator electrode(s) is adjusted to a value so that
redox processes could occur.
The current flowing between the indicator electrode
and a second electrode in the solution is measured.
There is a minimum potential required to initiate an
oxidation or reduction reaction at an electrode.
To effect a net Faradaic process the magnitude of
the applied potential must be sufficiently higher in
magnitude than the minimum.
Faradaic current proportional to the concentration
of the species undergoing transformation (redox).
A standard curve of current as a function of
concentration of a series of standard solutions is
prepared, and the concentration of the analyte is
determined from the curve.
Amperometry is also used to locate the end point in
an amperometric titration curve; a plot of current as
a function of titrant volume.
The shape of the curve varies depending on the
chemical species (titrant, analyte, products) that are
electroactive. The plot consists of linear regions
before and after the end point that are extrapolated
to intersection at the end point
Convention (i – V plots):
Y- axis: Cathodic currents positive direction (up)
X- axis: Negative potential increases to the right
Amperometric Titrations; Amperometric Titrations;
Reversible
Single polarizable id
X*
i Dual polarizable electroactive
electrode 0 electrodes i
X *, X’ *
E Vtit
Vtit
T + X →T’ + X’ T + X →T’ + X’
id T*
i

i T *, T’ *
E Vtit

T* Vtit
id i
X*

E Vtit
i X *, X’ *
id i T *, T’ *
T *

Vtit
E Vtit

Amperometry: Rotating Electrode:

Constant current mode

Eg. Ascorbic acid + I2 →

CC
Electrochemically
generated or
added in solution.

Monitor voltage required to

maintain a constant current.
It drops once unreacted I2
start accumulating in solution.

Volume, std I2

Voltammetry Three electrode cell

In voltammetry the current is measured as a function

of a varying applied potential at an electrode.

There is a minimum potential required to initiate an

oxidation or reduction reaction at an electrode.

Voltammetry is carried out in three electrode Background current (Ohms Law)

systems so that the potential applied to the or Residual current
working electrode can be accurately measured. Faradaic current
Charging current
 The structure of the electrode interface:

Unstirred solutions

Application of a sufficiently negative potential initiates Concentration profile

a reduction at the surface.

Oxidized material is removed by the reaction thus

the concentration near the surface drops.

Further, a more negative the potential depletion is

More, of the material further decreasing the
concentration at the surface.

Concentration gradients are created and at a

significant –ve value of the potential the concentration
at the surface will be nearly zero.

Reaction rate at the interface ~ current i. Voltammogram

A+(surface) + e → A Faradaic current*** id

electrochemical reaction
current

The overall reaction at steady state;

A+(bulk) → A+(surface) → A
slow fast Background – Ohm’s Law
V -ve

i ~ rate determining slow step

i increases with applied potential, reaches

a limiting value !! t
Linear sweep voltammetry
Slow step (mass transfer): Concentration profile

1. Migration
Movement of ions in an electric field. Contribution
to migration by analyte of interest, minimized by
adding a supporting electrolyte to the test solution.
2. Convection
Movement of bulk solution to the surface due to highest
thermal motion and stirring; is eliminated by concentration
gradient
using quiescent conditions (no stirring during
measurement)
3. Diffusion
Movement of analyte due to the concentration
gradient in the solution.

 ∂C 
i = nFADA  A 
 ∂x 
δ
Highest at the limiting current
(diffusion current).

Any further increase of potential

(negatively) does not increase
diffusion current.

 C − C A0 
id = nFADA  A  = k A (C A − C A ) = k AC A
0 0
Characteristic of
 δ  half reaction;
Half wave
potential

Note: background
Neglected.
 Note: oxidation reaction!!

Electrochemical reactions at the surfaces is an Polarography

interfacial phenomenon. It’s highly dependent of the
surface characteristics if the surfaces involved.

Any changes at the surface changes the i vs V curves.

The surface needs refreshing frequently.

It is achieved by employing the dropping Hg electrode.

A new Hg drop is created periodically and the

reaction done on a fresh surface (Polarography).
and it’s high over-potential allows use of larger -ve
limit of applied potential.

Ilkovic Equation
id = 706nD1/A 2 m 2 / 3t 1/ 6C A

n = number of electrons
DA = Diffusion coefficient cm2/s
m = flow rate of mercury mg/s
CA = conc. mM
t = time
Complications:
Spiky nature of the signal ~ noise.
Restructuring of charged species and molecules
at the interface, each time a new surface is created.
Polarogram (voltammogram dropping Hg electrode)
Single voltammogram can quantify many species if
sufficient separation between waves.

Polarographic experiments on a given surface Problems with dissolved O2 - must purge solutions
can be done only within a potential range. of dissolved O2.

At -ve limit, oxidation of water

2H2O→4H+ +O2(g) + 4e-

At +ve limit, reduction of water

2H2O+ 2e- →H2 + 2OH-

Useful media/voltage ranges

 Advantages of DME
(as opposed to stationary electrodes):

a. clean surface generated

b. rapid constant current achievement at drop growth
imeasured = ifaradaic + icharging c. remixing of solution when drop falls
d. high Hg overvoltage means even metals with high
Useless, contributes -ve E0 systems can be studied without H2 formation
to the background. e. amalgam formation more favorable vs. metal (s)
useful analytical component
Minimize as much as
possible.

Disadvantages of DME
Sampled current polarography:
a. Hg easily oxidized, limited use as anode (E =0.25V
vs SCE) 1. Create a drop (r = constant)
2Hg + 2Cl- →Hg2Cl4-2+ 2e- 2. Apply a ‘new’ potential (E/V)
b. non-faradaic residual currents limit detection >10-5 M 3. Delay for a time
c. cumbersome to use (toxic mercury) 4. Measure current (i)
d. sometimes produce current maxima for unclear 5. Repeat 1- 4.
reasons (use maxima suppressor)

drops faster with time!!!

 Pulsed Voltammetric Techniques:

Pulsed techniques takes advantage of the difference

in the rate of the decay of the charging and the
Faradaic currents following a potential step (pulse).

The charging current decays exponentially, whereas

the Faradaic current (for a diffusion-controlled current)
decays as a function of 1/√t.

The charging current is negligible 5 times the time

constant start of the pulse. The measured current is
predominantly Faradaic current, discriminating
between the Faradaic and charging currents.

Normal Pulse Voltammetry:

The potential wave form; a series of pulses of

increasing amplitude, potential returning to the
initial value after each pulse.

Differential Pulse Voltammetry:

E1/2 difference of ~0.2V resolvable.

Differential Pulse Voltammetry:

The potential wave form; small pulses (constant

amplitude) superimposed upon a staircase wave.
Current is sampled twice in each pulse period;
before the pulse, and at the end of the pulse.
The difference between these two current values is
recorded and displayed.

Detection Limit: 10-7 – 10-8M.

ip

E1/2

ip ∝ C

Square-Wave Voltammetry:

if

ir

≥5ms

Square-Wave Voltammetry:
The potential wave form; a square wave of constant
amplitude superimposed on a staircase wave form.
The current is measured at the end of each half-cycle.
The current measured on the reverse half-cycle (ir)
and subtracted from the current measured on the
forward half-cycle (if).
This difference current (if - ir) is displayed as a
function of the applied potential.
Anodic Stripping Voltammetry
In ASV, a mercury electrode is held at a sufficiently
negative potential to reduce metal ions in solution and
form an amalgam with the electrode.
The solution is stirred to during deposition of the
analytes (metal) referred to as pre- concentration step.
The reduced metals form amalgam with mercury.
After reducing and accumulating the analyte for some
period of time, td, allow a quiescence time and change
The potential on the electrode (increase) to re-oxidize
the analyte and generate a current signal; in NPV,
DPV or SWV ramps.
For a reduction process, with potential well positive
of the redox potential, both the forward
and reverse currents are zero, so the difference
current is also zero.
At potentials well negative of the redox potential,
the current is diffusion-controlled, and the
potential pulse has no effect; hence, the forward
and reverse currents are equal, and the difference
current is again zero.
The largest difference between the forward and
reverse currents (and hence the largest current
response) is at the redox potential.
Advantages to measuring the difference current.
1. Increase of the discrimination of the charging
current, since any residual charging current is
subtracted out.
2. The output of the current response is a symmetric
peak, rather than the sigmoidal curve typically
found for normal pulse voltammetry.
3. Easy resolution of peaks; E1/2 difference of ~0.05V
resolvable.
il t d
CA =
nFVHg
CA = concentration of analyte on ‘deposit’
il = limiting current at deposition
td = time of deposition
n =number of electrons for reduction
F = Faraday constant
VHg = volume of mercury (in the electrode)
The re-oxidizing (stripping) current ∝ CA ∝ CA,solution
Primary advantage of ASV is the pre-concentration
step of the analyte which allows to enhance output
signal (Detection limit 10-10 M).
Cyclic Voltammetry: Excitation Potential Current – Potential Response

A triangular waveform applied to the WE.

drop – due to
depletion of analyte
Linear wave forms used are increased and decreased diffusion too slow
in either anodic or cathodic fashion.
-ve

reduction
Eg. reverse reverse
υ

foward foward

Cyclic Voltammogram of A + ne = B
a reversible redox system.

oxidation

Epa

Epc
i pc = 2.69 ×108 n3/ 2 ACD1/ 2ν 1/ 2 E pa + E pc
E1/ 2 =
ipc = peak limiting current A 2
A = area of electrode m2
n =number of electrons for reduction
RT 59.0mV
C = concentration of analyte mol/L
D= Diffusion coefficient m2/s
E pa − E pc = =
υ = sweep rate V/s nF n
reversible

Irreversible
(not totally)

Karl Fisher Titration; water determination

Analysis of water is based on the quantitative reaction;

2B + I2 +B•SO2 + H2O → 2BH+I- + BSO3

BSO3 + ROH → BH+ R-OSO3-

I2 generated electrochemically via (i); 2I- → I2 + 2e

1mol I 2 ≡ 1mol H 2O ≡ 2 F
it
moles H 2O =
2F

i Bases: imidazole, diethanolamine

Alcohols: methanol, diethylene glycol monomethyl ether

2I- → I2 + 2e
I2 + 2e →2I- Organic solvent: chloroform, methanol, carbon
tetrachloride, formamide, ..

2I- → I2 + 2e
B, ROH, SO2,solvent, KI
LC-EC

V w.r.t reference