1

Introduction
 Electrolytic conductivity measures a solution’s ability to
carry an electric current.
 A current is produced by applying a potential between two
inert metallic electrodes (e.g., platinum) inserted into the
solution being tested.
 The change of electrolyte conductivity can indicate the
change of the concentration of the total ions,
 Defined as conductometric Analysis

2
 Principles
 Ohm’s Law states that the current I (amperes) flowing in a conductor
is directly proportional to the applied electromotive force E (volts) and
inversely proportional to the resistance R (ohms) of the coductor :
 = E / R
 The reciprocal of the resistance is termed the conductance; this is
measured in reciprocal ohms (-1) (Omega-1),
 The resistance of a sample of homogenous material, length L and
cross-section area a is given by :

R = Rho . L / a
Where  is a characteristic property of the material termed the resistivity (specific
resistance). 3
 The reciprocal of resistivity is the conductivity, Kappa ( specific

conductance)
 Which is the conductance of a one meter cube of substance and has the units -1 m-

, but if  in  cm , then  will be in -1 cm-1.

1

4
 The molar conductivity ( m ) (Lambda) is the conductivity per unit

molar conc of a dissolved electrolyte .

 =  / C

 The equivalent conductivity ( eq ) of an electrolyte is defined as the

conductivity due to 1gm equivalent of a solute contained between

electrodes spaced 1cm apart and is given by

 = 1000  / C
• Where C is the conc expressed in terms of normality of the solution, unit of  is -1 cm2 eq-1.

5
 The conductivity of electrolyte solutions is equal to the sum of
the conductivities of each type of ion present.

1- For a single dissolved salt, equivalent conductance can be

expressed as
 = + + ‑
where + = the equivalent conductance of the cation
- = the equivalent conductance of the anion

2- For mixtures, would be equal to the sum of equivalent

conductances of all the individual ionic species ( + 's & - 's )

6
 The equivalent conductance of salts or ions increases as the
concentration decreases.
 At infinite dilution there are no disturbing effects on the mobilities
of the ions other than variations in solvent and temperature, and the
equivalent conductance reaches its maximum value.
 The equation may be rewritten as:

0 = +0 + -0
Where 0 = the equivalent conductance of the electrolyte at infinite dilution.

+0 = the limiting ionic equivalent conductance of the cation at infinite dilution.

-0 = the limiting ionic equivalent conductance of the anion at infinite dilution.

7
 Conc.of NaCl 0.1 0.01 0.001 infinite dilution
Λ 106.7 118.5 123.7 126.4

Increasing direction

Infinite dilution = null inter ionic attraction

 At infinite dilution the ions act completely independently

8
Table: Values of the limiting ionic molar conductivities for some ions in water at 25 C

No Cations Λ0+ Anions Λ0-

1 H+ 349.8 OH- 198.3
2 Na+ 50.1 F- 55.4
3 K+ 73.5 Cl- 76.3
4 Li+ 38.7 Br- 78.1
5 NH4+ 73.5 NO3- 71.5
6 Ag+ 61.9 HCO3- 44.5
7 N(CH3)4+ 44.9 CH3COO- 40.9
8 Ca2+ 119.0 (59) CO32- 138.6 (69.3)
9 Mg2+ 106.2 (53.1) SO42- 160.0 (80)
10 Cu2+ 107.2 (53.6) PO43- 240 (80)
11 Zn2+ 105.6 (52.8) 9
 Dissociation / Association

 The equivalent conductance of a completely dissociated solute in

solution is normally referred to as the equivalent conductance at
infinite dilution, Λo.
 As the solution becomes more concentrated, Λ decrease so degree of
ionization or dissociation, α is

α = Λ / Λo
 For a weakly ionized substance, Λ varies much more markedly with
conc. b/c the degree of ionization, α, varies strongly with conc.

10
 The equivalent conductance, however, must approach a
constant finite value at infinite dilution, Λ0, which again
corresponds to the sum of the limiting ionic conductance’s.

 Λ0 for a weak electrolyte can be deduced from Λ0 values

obtained for strong electrolytes,

 Let us consider acetic acid (HAc) as a typical weak electrolyte

Λ0 (HAc) = Λ0 (HCl) + Λ0 (NaAc) - Λ0 (NaCl)  

11
 The measurement of conductivity

Conductivity measurement is performed with wheat

stone bridge circuit and alternating current source.
Cells: electrode consists of a pair of platinum plates
that are firmly anchored with in the cell to assure
constant spacing.

12
 The specific conductivity is the conductance of a cube of
material, 1 cm on each edge.
 Since it is difficult to build a cell with well defined
geometrical parameters A & l, any cell should be calibrated
with a solution of exactly known specific conductance,
 The cell factor or cell constant, c
c =R =l/A= length/electrode area
 The cell constant, c, with unit’s m-1, is determined by
measuring the resistance of a cell filled with a solution of
known conductivity, which is invariably KCl (0.002M).
13
Thus if c=1, the observed resistance is equal
numerically to the reciprocal of the specific
conductance of the solution used .
Once c has been determined for a cell, then the
measurement of the resistance of any other solution
will provide values of Λ or .

14
 Conductometric Titrations
 Rate of change of conductance as a function of added titrant used to
determine the equivalence point.

Note that:

1- The relative change of conductance of the solution during the reaction

and upon the addition of an excess of reagent largely determines the
accuracy of the titration.

2- Large amounts of foreign electrolytes, which do not take part in the

reaction, must be absent, since these electrolytes have a considerable
effect upon the accuracy.
15
 Applications of conductometric measurements
1. Direct measurement of conductivity is a very sensitive
procedure for measuring ionic concentrations.
 It must be used with caution since any charged species present in

a solution will alter the total conductance.

2. Conductometric measurements can also be used to

ascertain the end point in many titrations.

3. Purity of distilled or de-ionized water is commonly checked

by conductance measurement.
 Conductivity of pure water is about 5X10-8.

16
 Applications...

4. Conductometric monitoring of rivers and lakes water is

used to control pollution, conductometric measurements
are performed to determine salinity values.

5. Conductivity cells can be coupled to ion chromatographic

systems to provide a sensitive method for measuring ionic
concentrations in the eluate.

17
 Applications of the conductometric titrations
1- Strong acid with a strong base :
 The conductance first falls, due to the replacement of the hydrogen ions ( 350) by the added
cation ions ( 40 - 80) and then, after the equivalence point has been reached, rapidly rises with
further additions of strong alkali due to the large  value of the hydroxyl ions ( 198 ). The two
branches of the curve are straight lines provided that the volume of the reagent added is
negligible, and their intersection gives the end point.

H+ from strong acid HA

Conductance

OH- from strong base BOH

BA salt

ml of the base
e.p. 18
 2- Strong acid with a weak base :
 The titration of a strong acid with a moderately weak base may be illustrated by the
neutralization of dilute sulfuric acid by dilute ammonia solution. The first branch of the
graph reflects the disappearance of hydrogen ions during the neutralization, but after
the end point has been reached the graph becomes almost horizontal, since the excess
aqueous ammonia is not significantly ionized in the presence of ammonium sulfate.

H+ from strong acid HA

Conductance

Salt BA OH- from weak base BOH

ml of base

e.p.
19
 NaOH
3- Weak acid with a strong base:
 The shape of the curve will depend upon the conc. Acetic acid

Conductance
and ionization of the acid. Thus the neutralization 0.
1
of the acetic acid with NaOH solution, the salt which 0. M
0 1
is formed during the first part of the titration tends M
0.
to repress ionization of acetic acid still present so 00
1
M
that its conductance decreases. The rising salt conc
(w/c is ionized) will, however, tend to produce an ml of base
increase in the conductance. AC- + H2O = HAC +
OH-
 In consequence of these opposing influences the
titration curves may have minima, the position of

Conductance
which will depend upon the conc. and strength of the
weak acid. As the titration proceeds, a somewhat
indefinite break will occur at the end point, and the
graph will become linear after all the acid has been
neutralized.
 Generally titrations of weak and moderately strong
acids with a strong base are suitable for ml of base
conductimetric techniques. 20
 4- Weak acids with weak bases:
 Titration of a weak acid with a weak base
can be readily carried out, and frequently it
is preferable to use this procedure rather
than use a strong base.
 The neutralization curve up to the

conductanc
equivalence point is similar to that
obtained with NaOH since both Na &
NH3
amm. acetates are strong electrolytes, after
the e.p. an excess of aqueous ammonia
solution has little effect upon the
conductance as its ionisation is depressed
by the ammonia salt present in the soln.
 The advantages over the use of strong ml of base
alkali are that the e.p. is easier to detect.

21
 5-Mixture of a strong acid & a weak acid with a NaOH
HCl
strong base :
 Upon adding a strong base to a mixture of a strong
acid and a weak acid (e.g. HCl & CH3COOH), the
conductance falls until the strong acid is neutralised, CH 3COOH
the rises as the weak acid is converted to its salt and
finally rises more steeply as excess alkali is
introduced.
Note that;
1- Increasing ionisation of the weak acid results in a
rounding-off at the first e.p. (HCl)
2- hydrolysis of the salt of the weak acid causes a
rounding-off at the second e.p. (CH3COOH)
HCl
3- Extrapolation of the straight portions of the three
branches leads to definite location of the end points.

6- Titration of the same mixture with a weak base NH4OH

OH
CO
CH 3
e.g. ammonia solution is frequently preferable to strong
alkali for reasons already mentioned in discussing
weak acids.

22
Coulometry

23
Coulometric Methods of Analysis
 Measures quantity of electricity or the charge generated by a
reaction at an electrode.
 Coulometry is a term derived from “Coulomb” that units
used for measuring quantity of electricity
 Coulometric analysis is an application of Faraday’s First
Law of Electrolysis which states that:
 The current or charge passed through an electrode in a redox
reaction is proportional to the moles of the reaction’s
reactants and products.
24
Faraday’s law:
 Total charge, Q, in coulombs passed during electrolysis is related to
the absolute amount of analyte:

Q  nFN
QM
m 
Fn

 Charge (Q) is related to current (I) according to:

Q = It (constant current)
Q = ∫ I dt (controlled potential)

Where n = #moles of electrons transferred per mole of analyte

F = Faradays constant(96487 C /mol) N = no. of moles of analyte
M = molecular mass I = current (A) t = time (s)
25
 What do we measure in coulometry?
 Current and time.

 Q & N are then calculated according to one of the above

equations

 Coulometry requires 100% current efficiency.

 What does this mean?

 All the current must result in the analyte’s oxidation or

reduction (for accurate result).

26
 Two types of coulometric methods

 Controlled-potential coulometry - Potentiostatic coulometry

 A constant potential is applied to the electrochemical cell

 Current initially high but decreases

 Measure electricity needed for redox

 Controlled-current coulometry - Coulometric titration

 Titrant is generated electrochemically by constant current passed

through the electrochemical cell.

 Concentration of the titrant is equivalent to the generating current

27
 1. Controlled-Potential Coulometry

The current flowing through an electrochemical cell

under a constant potential is proportional to the analyte’s
concentration.
As electrolysis progresses the analyte’s concentration
decreases, as does the current.
The resulting current-versus-time profile is shown in
Fig. Below.

28
 Background current

Fig. Current versus time for a controlled-potential coulometric analysis.

The measured current is shown by the red curve. The integrated area under
the curve, shown in blue, is the total charge.
29
 2. Controlled-Current Coulometry
 Also known as: amperostatic coulometry or
coulometric titrimetry
 When called coulometric titration, electrons serve as the titrant.

Fig. Current versus time for a controlled-current coulometric analysis.

The integrated area under the curve is the total charge.
30
 Constant current electrolysis is used to generate reagent which
reacts stoichiometrically with the substance to be determined.
 The quantity of the substance reacted is calculated with the aid
of Faraday’s law and the quantity of electricity passed can be
evaluated simply by timing the electrolysis at constant current.
 In coulometric titrations, titrant is generated electrically (not
added from a burette) and its amount is evaluated from a
knowledge of the current and the generating time.

31
Fundamental requirements of a coulometric titration are:

1- Reagent-generating electrode reaction must proceeds with 100%

efficiency.

2- Generated reagent must reacts with the substance being

determined stoichiometrically and rapidly.

32
Advantages of coulometric titrations:

1-External standard solutions are not required.

2- Unstable reagents such as Br2, Ag+ and Ti3+ can be used safely as standards
(They are generated and consumed immediately)

3- The method is ideally applied for micro and semi-micro scale titrations
without the well known difficulties involved in the standardization and
storage of very dilute solutions.

4- The effect of impurities in the generated solutions is minimal.

5- The method is adapted to remote control and also to automatic control

because of the relative ease of the automatic control of the electric
current. 33
 Coulometric titrimetry has two advantages over
controlled-potential coulometry.
 First, using a constant current makes for a more rapid

analysis since the current does not decrease over time.

 Thus, a typical analysis time for controlled current coulometry is
less than 10 min, as opposed to ~ 30–60 min for controlled-
potential coulometry.

 Second, with a constant current the total charge is simply the

product of current and time.

 A method for integrating the current–time curve, therefore, is not
necessary.

34
* Using a constant current does present two important
experimental problems that must be solved if accurate results are
to be obtained.
 First, as electrolysis occurs the analyte's concentration and,
therefore, the current due to its oxidation or reduction steadily
decreases.
 To maintain a constant current the cell potential must change until

another oxidation or reduction reaction can occur at the working

electrode.
 Unless the system is carefully designed, these secondary reactions

will produce a current efficiency of less than 100%.

35
 Second problem is the need for a method of determining
when the analyte has been exhaustively electrolyzed.
 In controlled‑potential coulometry this is signaled by a decrease in the

current to a constant background or residual current.

 In controlled‑current coulometry, a constant current continues to flow

even when the analyte has been completely oxidized or reduced.

 A suitable means of determining the end‑point of the rxn, te, is needed.

 i.e Indicator used to determined end point

36
Methods for detection of end points in coulometric titrations:

 Use of chemical indicators (must be not electro-active)

 Potentiometric detection of end points.

 Amperometric detection of end points.

 Spectrophotometric detection of the end points.

37
 Application of Coulometric Method
 Used for the determination of inorganic cations and anions,
including trace metals and halides,
 It also can be applied to the quantitative analysis of organic
compounds, like trichloroacetic acid
Cl3CCOO–(aq) + H3O+(aq) + 2e– ↔ Cl2HCCOO–(aq) + Cl–(aq) + H2O(l)

 Controlled-current coulometric method is relatively easy to

measure small quantities of charge, coulometric titrations can

be used to determine small quantities of analyte that cannot be
measured accurately by a conventional titration.
38
 Examples
1. 0.5 A was used to deposit Cu2+ in 10 mins in the Daniell
Cell, the amount of copper in solution (Cu = 63.5 g/mol, F = 96,485
C/mol e- ):

m = QM
nF

m = QM = (0.5 A x 10 mins x 60s/min) x 63.5 g/mol

nF 96,485 C/mol e- x 2 e-

m = = 9.87 x 10-2 g

39
2. Suppose that the ff cell, producing a constant
voltage of 1.02V, is used to operate a light bulb
with a resistance of 2.8Ω.
Zn(s)|Zn2+(aq)||Cu2+(aq)|Cu(s)
 How many hours are required for 5.0g of Zn to be
consumed? (MWZn=65.4)

Solution
 The anode rxn is: Zn(s) → Zn 2+ + 2e-
Q= nFN = 2×96485×5/65.4 =1.48×104C
 The current flowing via the circuit is:
I=E/R =1.02V/2.8Ω = 0.364A
 Time: t = Q/I = 1.48×104C/0.364A
= 4.06×104s = 11.3h
40
3. A 0.3619-g sample of tetrachloropicolinic acid,
C6HNO2Cl4 (MWt= 261), is dissolved in distilled
water, transferred to a 1000-mL volumetric flask,
and diluted to volume. An exhaustive controlled-
potential electrolysis of a 10.00-mL portion of this
solution at a spongy silver cathode requires 5.374 C
of charge. What is the value of n (moles of elecrons)
for this reduction reaction?
Solution
 The 10.00-mL portion of sample contains 3.619 mg,
i.e N = 1.39 × 10–5 mol of tetrachloropicolinic acid.

41
42
To determine the purity of a sample of Na 2S2O3, a
sample is titrated coulometrically using I – as a mediator
and I3– as the titrant. A sample weighing 0.1342 g is
transferred to a 100-mL volumetric flask and diluted to
volume with distilled water. A 10.00-mL portion is
transferred to an electrochemical cell along with 25 mL
of 1 M KI, 75 mL of a pH 7.0 phosphate buffer, and
several drops of a starch indicator solution. Electrolysis
at a constant current of 36.45 mA requires 221.8 s to
reach the starch indicator endpoint. Determine the
sample’s purity.
43
44
45
Polarography

46
 VOLTAMMETRY

 A technique which concerned with the study of voltage,

current-time relationships during electrolysis in a cell.
 A time-dependent potential is applied to an electrochemical
cell and the resulting current is measured as a function of that
potential.

47
 VOLTAMMETRY…
 General principles:

 As potential is applied, electrolysis of analye begins and current rises until

it reaches limiting current

 Plot of I vs. E is called a voltammogram

 Diffusion current = difference between background I and limiting I

 E1/2 = half wave potential (characteristic of every redox reaction)

Id = kC
Where Id = Diffusion current,

k = constant,

C = conc. of analyte

48
A simple classification of voltammetric methods is
based on the electrode type.
Polarography - voltammetric technique that uses
dropping mecrury electrode (DME) as working
electrode.

49
 Polarography
 A form of voltammetry using a dropping mercury electrode.

 The DME consists of a glass capillary through which mercury flows

under gravity to form a succession of mercury drops.
 The plot of the applied potential vs corresponding current is called
polarogram / polarographic wave and the apparatus used for
determinations was called polarograph.

50
 Instrumentation
 It is usually composed of three electrodes:

1. Working electrode: microelectrode whose potential is varied with time

2. Reference electrode: potential remains constant (Ag/AgCl electrode or

calomel)

3. Counter (auxiliary) electrode: Hg or Pt that completes circuit, conducts e-

from signal source through solution to the working electrode
 In some cases only two electrodes are used ( working and reference) e.g. in
complete aqueous medium where the resistance for the current flow is very
small, but usually three-electrode cell is used.

51
 R

SCE DME

P
V

Counter
Electrode Fig. Polarographic apparatus
DME - Renewable surface

53
 Advantages of dropping mercuric electrode

 Its surface is reproducible, smooth and continuously renewed , this

eliminate the poisoning effect.
 Mercury forms amalgams ( solid solution) with many metals.
 The diffusion current assumed a steady value immediately after
each change of applied potential and is reproducible
 The large hydrogen over-potential of mercury renders possible
deposition of substance that difficult to reduce
 e.g. alkaline metals, Al+3, Mn+2 etc which are not easily amenable to
platinum microelectrode.

 The surface area can be calculated from the weight of the drop.
 Disadvantages of dropping mercuric electrode

 At potential more positive than +0.4V vs SCE, mercury dissolve

and producing anodic polarographic wave which masks the other
waves of other oxidizable species in the solution, so d.m.e can be
used only for the analysis of reducible or easily oxidizable
substance.
 The capillary is very small in size so easy to blocked and so all
process stopped.
 The presence of impurities in the sample or in mercury cause
blockage of the capillary results in malfunction of the electrode.

55
Supporting electrolyte:
 It is a solution of indifferent electrolyte ( base or ground electrolyte)
which by itself don’t oxidized or reduced at working electrode at the
selected potential range.
 It raises the conductivity of the solution and carry the bulk of the
current so prevent the migration of electro-active materials (sample
material to be determined) to the working electrode.
 It may control or (buffer) the level of hydrogen ion activity in
solution.
Atypical current-voltage curve (polarogram) is shown in the following figure:
 From A to B, practically no current will pass through the cell.
 At B, when the potential of the working electrode (DME) is equal to the deposition
potential of the cadmium ions with respect to metallic cadmium electrode, the current
suddenly increases and the working electrode becomes depolarized by the cadmium
ions, which are then discharged upon the electrode surface to form metallic cadmium;
consequently a rapid increase in the current flowing through the cell occur.
 At point C, the current no longer increase linearly with the applied potential but
approaches a steady limiting value.
 At point D no increase in current is observed at higher cathode potential unless a
second compound ,able to depolarize the working electrode , present in the solution.
Decomposition potential

rrent
Current (microampers)

C Limiting cu
D

Diffusion current
si d ual c urrent
Re B
A
Half-wave potential Applied potential (volts)
Note that:
 The distance between B and C usually known as Polarographic wave.

 The potential corresponding to the middle of the polarographic wave is known as

half-wave potential.
 The number of cadmium ions reaching the cathode surface as a result of migration and

diffusion from the main bulk of solution always exceeds the number of cadmium ions
which reacted and deposited on the cathode surface.

 At the point C the rate of supply of cadmium ions from the main bulk of the
solution to the working electrode has become equal to the rate of their
deposition and no further increase in current passing through the cell is expected
with increasing the potential.
 The polarogram is characterized by different parameters :

1-Residual current: at small applied potential only a residual current flow in the cell which
caused by the presence of impurities in the supporting electrolyte or sample.

2-Limiting current: is the region on the polarogram in which the current after increased
sharply , becomes essentially independent on the applied potential .

3-Diffusion current: it is the difference between limiting and residual currents . It is directly
proportional to the concentration of the reactive substance.

4- Half wave potential (E1/2) : is the potential at which the current is equal to one half the
diffusion current. It is a characteristic of the nature of the reactive material, independent on
concentration, depend on pH of the medium, type of supporting electrolyte and type of
electrode.

5- Decomposition potential: is the potential at which the substance begin to oxidize or reduce.
 Diffusion current
 When the potential applied to a polarographic cell exceeds the decomposition potential of an
electrolyte species, its concentration at the surface of the electrode (d.m.e.) is immediately
diminished.
 A conc gradient is therefore established and more of that species diffused from the bulk
solution to the electrode surface (Fick’s law of diffusion) .
 The resulting current flow is proportional to the rate of diffusion

i  ( C - Co) or i = K (C - Co)
 where C and Co are the conc of the electro-active species in the bulk solution and at the surface of

electrode respectively.

 By increasing the applied voltage, reduction occurs more rapidly and (Co) becomes zero and the
conc gradient reaches a maximum.
 At this point, the rate of the diffusion and the current flowing in the cell reach to their limiting
values.

i = KC Figure
 Ilkovic Equation:

 It is the equation that relates the various parameters that determine the
magnitude of the diffusion current obtained with a dropping mercury electrode

id = 607 n D1/2 m2/3 t1/6 C

where
 id = average diffusion current measured in micro-ampers.
 n = number of electrons consumed in the reduction of one molecule of the electro-active
species (the sample).
 D = diffusion coefficient of the reducible or oxidizible substance expressed in Cm 2/second.
 m = rate of flow of mercury from the dropping mercuric electrode expressed in mg/second.
 t = drop time in seconds.
 C = concentration in mol/liter.
 The constant 607 is a combination of natural constants including the Faraday’s constant, it is
slightly temperature-dependent and this value (607)calculated at 25 C.
When an external electromotive force (e.m.f.) is applied to a cell that

containing solution of substance that can be reduced e.g. CdCl2,

All the positively charged ions present in the solution will be attracted to the negative
working electrode by:

- Electrical force; due to the attraction of oppositely charged bodies to each other.

- Diffusive force; arising from the concentration gradient produced at the electrode
surface.

The total current passing through the cell can be regarded as the sum of these two
factors.

the following reaction will occur during the reduction process at the surface of
cathode
 Cd+2 + 2e + Hg0 == Cd0(Hg0)
 Potential applied on the working electrode is usually swept over (i.e. scan)
a pre-defined range of applied potential
0.001 M Cd2+ in 0.1 M KNO3 supporting electrolyte
Electrode become more and more
reducing and capable of reducing Cd 2+
All Cd2+ around the electrode has
Cd 2+
+ 2e Cd-
already been reduced. Current at
Current starts to be registered at the the electrode becomes limited by
i (A)
electrode the diffusion rate of Cd2+ from the
Working electrode is E½ bulk solution to the electrode.
no yet capable of Thus, current stops rising and
reducing Cd2+  levels off at a plateauid
Current at the working
only small residual
electrode continue to rise as
current flow through
the electrode become more
the electrode Base line
reducing and more Cd2+ around
the electrode are being of residual
reduced. Diffusion of Cd2+ current
does not limit the current yet

-0.2 -0.4 -0.6 -0.8 -1.0 -1.2 -1.4

V vs SCE
 Application of polarography:
A-Qualitative application
 This technique can be used for the determination of equilibrium constant
and reaction rate.
 Elucidation of reaction mechanism coupled with the actual electrode
process.
 Study the reversibility of the reaction.

 Useful also for stability studies and study the connection between
polarographic properties and physiological activities of drugs.
B-Quantitative application
 Polarography ( voltammetry) can be used for determination of the
conc. of the electro-active compounds by direct measurements of the
diffusion current.
 It can be used in combination with other technique e.g. HPLC to
determine the concentration of substances presents in minute
amounts especially in biological fluids.
66
 Voltammetric analysis
 Analyte selectivity is provided by the applied potential on the working electrode.

Pt working Ag counter
electrode at -1.0 electrode at
V vs SCE 0.0 V

Pb2+ + 2e- Pb EO = -0.13 V vs. NHE AgCl Ag + Cl-

K+ + e- K EO = -2.93 V vs. NHE SCE

X M of PbCl2
0.1M KCl
 -1.0 V vs SCE Concentration gradient created
Pb2+ + 2e- Pb
between the surrounding of the
electrode and the bulk solution
K+
Pb2+ Pb2+ K+
K+ Pb 2+

Pb2+
K+ K+ Pb 2+
K+
K+ K+
Pb 2+
K
+

Pb2+
Pb2+ K+ Pb2+
K+ Pb2+ K+
K+
K+
Pb 2+
K +

K+ Pb2+ Pb 2+ K+ Pb2+
K+Pb2+ migrate to
the electrode
K+
K + via diffusion Pb2+
Pb 2+
Pb2+ K+
Pb2+
Pb2+
K+ Pb2+ Pb2+
K +
K+
K+ K+

Layers of K+ build up around the electrode stop the

migration of Pb2+ via coulombic attraction