Lecture 9

Non- potentiometric methods of analysis

Dr. Rasha Hanafi

Dr. Rasha Hanafi, GUC PHCM662; Lecture 7; 25-03-2013 1

 Objectives

1.Identify fundamentals of electrolysis.

2.Determine voltage changes when current flows.
3.Estimate overvoltage due to different types of polarization.
4. Describe controlled potential electrolysis with three electrode
system.
5. Use electrogravimetric measurement for quantitative analysis.
6. Use coulometry and coulometric titrations for quantitative
analysis

Dr. Rasha Hanafi, GUC PHCM662; Lecture 7; 25-03-2013 2

 I. Potentiometric versus non-potentiometric
methods of analysis

Galvanic cell Electrolytic cell

Dr. Rasha Hanafi, GUC PHCM662; Lecture 7; 25-03-2013 3

 I. Potentiometric versus non-potentiometric methods of
analysis
Potentiometric methods
1. No external work (potential) is
applied.
2. Spontaneous chemical reaction.
3. No current passes due to the
presence of a high resistance in the
potentiometer, hence no change in
conc. of analytes happen, so
potentiometry is a non-destructive
method of analysis.
4. The thermodynamic potential Ecell is
calculated from Nernst equation to
be used in quantitative calculations.
5. By convention, right position
represents always the anode.
Dr. Rasha Hanafi, GUC PHCM662; Lecture 7; 25-03-2013
Non- potentiometric methods
1. External work is applied: an external
battery is needed. Current is measured
by an ammeter. The moles of e- flowing
through the cell are “It/F” (I:current,
t:time and F: Faraday constant 9.6x104
C/mol).
2. The chemical reaction is not
spontaneous and is forced to occur.
3. Positions are not important : connections
of the poles of the battery control which
will be the anode.
4. Consumption of analytes happen
(analysis is destructive).
5. The potential of the cell can not be
simply calculated from Nernst equation:
current flow affects the potential
measured.
4
 II. Fundamentals of electrolysis
Suppose we dip Cu and Pt electrodes into an aqueous solution of
Cu2+ and pass electric current through to deposit Cu2+ as Cu metal
at the cathode which necessarily liberates O2 at the anode.

cathode Cu 2  2e   Cu ( s)
Anode H 2O  12 O2 ( g )  2 H   2e 
Net reaction H 2O  Cu 2  Cu ( s)  12 O2 ( g )  2 H 

The electrode at which the reaction

cathode
of interest occurs is called the anode
working electrode (Cu-electrode),
while the other electrode is called CuSO4(aq)

the counter/ auxiliary electrode.

Two-electrodes cell
Dr. Rasha Hanafi, GUC PHCM662; Lecture 7; 25-03-2013 5
 II. Fundamentals of electrolysis, cont.
• Note that a negative potential is applied to the cathode where reduction occurs and a
positive potential is applied to the anode where oxidation occurs.

• For the aforementioned cell: Ecell = Ecathode  Eanode

If the cell contains 0.2 M Cu2+ and 1.0 M H+ and liberates O2 at a pressure of 1.0 bar, the
thermodynamic or equilibrium cell potential will be E= 0.911 V (calculated using Nernst
equation for the cell reaction as written). Thus the reaction has a negative potential which
means that the reaction is not spontaneous.

• If we apply a voltage slightly greater than 0.911 V between the electrodes, we will provide
just enough free energy to force the reaction.

• If higher current is needed (higher reaction rate), an extra voltage (overvoltage) is needed
(Faraday 1st law of electrolysis: The mass of a substance altered at an electrode during
electrolysis is directly proportional to the quantity of electricity transferred at that
electrode).
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 III. Voltage Changes when current flows

When current passes (at a fixed applied potential, battery of fixed

voltage) through an electrochemical cell, the measured cell
potential departs from that derived from thermodynamic
calculations (using Nernst equation)!!
This is due to phenomena such as
1.Ohmic resistance.
2.Polarization effects :
A. Concentration polarization .
B. Charge-transfer polarization.

Dr. Rasha Hanafi, GUC PHCM662; Lecture 7; 25-03-2013 7

 III. 1. Ohmic resistance
 It is the potential needed to overcome the resistance of the ions to
move toward the anode and the cathode i.e., to overcome the electric
resistance (R) of the solution in the electrochemical cell when current
is flowing.
The resistance, R, depends on the kinds and
Eohmic = I R concentrations of ions in solution
 The effect of IR drop is to decrease the measured potential of a
galvanic cell (make it less positive):

Ecell = Ecathode  Eanode  I R, if no current passes I=0 IR=0

 Thus, we have to increase the potential to operate an electrolytic cell
(make it more powerful = more negative).

Dr. Rasha Hanafi, GUC PHCM662; Lecture 7; 25-03-2013 8

 III. 2. Sources of polarization
For the half-cell shown in figure, the overall electrode reaction is:

Ox + ne Red Ex: Cu2+ + 2e Cu

Bulk Bulk
For current to pass continuously across the
surface of the electrode, Ox in the bulk of Steps of electrochemical reaction
solution should diffuse to the electrode
region in what is known as mass transfer Electrode surface Solution bulk
step followed by electron transfer step Mass transfer
when Ox reaches the electrode surface. Ox Ox
The electrochemical reaction is completed ne
when the formed Red diffuses back to the Electron
transfer
bulk of solution. If one of these steps is
slow, it will limit the overall rate of Red Red
reaction and thus reduces the magnitude Mass transfer
of current.
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 III. 2. A. Concentration polarization
 It arises when the transport of reactive species to the electrode surface is
insufficient (slow mass transfer) to maintain the current needed by the
equation:
Ecell = Ecathode  Eanode  I R
 It is observed when concentrations of the electroactive species are not the
same at the surface of the electrode as in the bulk solution
0.0591
 In case of Cu2+: E cathode  0.34  log [Cu 2 ]s
2
where [Cu2+]s is the concentration of Cu2+ at the electrode surface

 If the reduction of Cu2+ occurs rapidly (fast electron transfer, [Cu2+]s will
decrease because Cu2+ ions cannot diffuse to the electrode surface as fast as
they are consumed (slow mass transfer). Thus, a concentration polarization is
observed: Ecell = Ecathode  Eanode  I R  c

 Consequently, a concentration overvoltage, c, should be applied in order to

increase the rate of mass transfer step from the bulk of solution to the
electrode surface.
Dr. Rasha Hanafi, GUC PHCM662; Lecture 7; 25-03-2013 10
 III. 2. A. Concentration polarization, cont.
 In order to know how concentration polarization can be prevented or induced as
required, it is important to investigate the mechanisms by which ions are transported
from the bulk of solution to the electrode surface.
 An electroactive species has three ways to reach the surface of an electrode:
1. Diffusion through a concentration gradient. Whenever a concentration
difference develops between two regions of solution, as it does when a species
is reduced at a cathode surface (or oxidized at an anode surface), ions move
from the more concentrated region to the more dilute as a result of diffusion.
2. Migration, the process by which ions move under the effect of an electrostatic
field where they are attracted or repelled by a charged surface.
3. Convection, which is the movement of bulk fluid by mechanical means such as
stirring or agitation.

 Concentration polarization is observed when diffusion, migration and

convection are insufficient to transport the reactant to or from electrode
surface at a rate demanded by the theoretical current.
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III. 2. B. Activation or charge transfer polarization
After application of external
potential
It arises when the rate of the oxidation or
reduction reaction at one or both electrodes is
not rapid enough (slow charge transfer) to
yield currents demanded by the theory.
So, an activation overvoltage, a, is needed to
activate the reactant to pass across the
electrode surface and to facilitate the charge
transfer step.

To sum up, Ohmic resistance, concentration and activation polarization

make electrolysis more difficult. They make the cell potential more
negative (decrease the potential of galvanic cell).
Ecell = Ecathode  Eanode  IR  c  a
As a result more voltage (overvoltage) is needed from the power supply
to drive the reaction of the cell forward.
Dr. Rasha Hanafi, GUC PHCM662; Lecture 7; 25-03-2013 12
 Today’ s lecture

Dr. Rasha Hanafi, GUC PHCM662; Lecture 7; 25-03-2013 13

 III. 3. Controlled potential electrolysis with 3-electrode cell
• In general we need to adjust the potential of the working electrode so that some
electroactive species react while others do not.
• Metal working electrodes are generally polarizable, which means that their
potentials easily change when small current flow.
• On the other hand, a reference electrode is said to be non-polarizable, because its
potential does not vary with the flow of current.
Thus, in order to measure and control the potential of
a polarizable working electrode, a third reference
electrode should be introduced
 The working electrode is the one at which the
reaction of interest occurs
 The reference electrode is used to measure
the potential of the working electrode
 The auxiliary electrode (the counter electrode)
is the current supporting partner of the
working electrode.
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III. 3. Controlled potential electrolysis with 3-electrode cell, cont.
• In three electrode configuration, a potential is applied between the auxiliary and
working electrodes and the potential of only the working electrode (measured with
respect to the reference electrode) is monitored.

• In controlled potential electrolysis, The voltage difference between the working

electrode and reference electrode in a three-electrode cell is adjusted by an electronic
device called potentiostat.
Example: Analysis of Cd2+ and Pb2+ mixture

•If the applied potential is set at E1, the

respective potential on the working

Current
Pb2+ Pb
electrode will be sufficient to deposit only
Cd2+ ions via reduction to Cd.
Cd2+ Cd
•If the potential is adjusted at more
negative value of E2, both cations will be
E1 E2
deposited simultaneously. potential
-ve
Dr. Rasha Hanafi, GUC PHCM662; Lecture 7; 25-03-2013 15
 III. 3. Control of the applied voltage
• Nothing special happens at -0.911 V Observed current-voltage relationship for
(voltage calculated from Nernst). At this electrolysis of 0.2 M CuSO4 solution
low voltage, a small residual current is
observed as a result of reduction of traces
of dissolved O2 or some Fe3+ impurities.
• Near 2.0 V, electrolysis of Cu2+ starts and
the rate of reaction (the reduction current)
increases steadily.
Cu2+(aq) + 2e- Cu(s)
• The voltage between the two electrodes is
E = Ecathode  Eanode  IR  overpotential
Suppose we hold the applied voltage at E = 2.0 V until all Cu2+ is reduced . As
Cu2+ is used up (at the end of electrolysis), the current decreases and both the
ohmic and overpotentials decrease. Note that Eanode is fairly constant because of
the high concentration of solvent (H2O) being oxidized at the anode. Since the
applied voltage was held constant, Ecathode eventually becomes more negative in
order to keep the integral equality in the above equation.
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 III. 3. Control of the applied voltage, cont.

• When the applied potential is held constant, the

potential of the cathode may become negative
enough that unintended reductions may occur:
1. reduction of H+ or water to H2 gas. The gas bubbles
evolved at the cathode surface interfere with the
deposition of the solid.
2. reduction of other ions such as Co2+, Sn2+ or Ni2+.

• To prevent the cathodic potential from becoming so negative, a cathodic

-
depolarizer such as NO3 can be added to the solution. It is more easily
reduced than H+ or any other interfering species.
 
NO3  10H   8e   NH 4  3H 2 O

• Alternatively, we can use three-electrode cell with potentiostat to control the

cathodic potential and prevent unwanted side reactions.

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 IV. Electrogavimetric Analysis
• The analyte is quantitatively deposited on an electrode by electrolysis.
• The electrode is weighed before and after deposition, the increase in mass quantifies
the analyte.
 Cu2+ in solution can be quantified by reducing it to Cu(s)
on a carefully cleaned Pt gauze cathode with a large
surface area. O2 is liberated at the counter electrode
(decomposition of water).
 How do you know electrolysis is complete?

1. disappearance of color in solution (if the analyte

solution is colored).
2. to remove one drop of solution and perform a
qualitative test for analyte confirming its total
absence.

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 V. Coulometry
Coulometric titration (const. current): 2Br   Br2  2e  (Generation of Br2 titrant)

 form of quantitative analysis based on Br

counting the electrons used in a reaction. Br2

 Ex: cyclohexene (CYC) can be titrated with Br

cyclohexene trans-1,2-dibromocyclohexane
Br2 generated by electrolytic anodic analyte
-
oxidation of Br .
 The initial solution contains an unknown
quantity of CYC and a large amount of Br-.
 The reaction is carried out at constant
current. Br2 generated at the Pt generator
anode immediately reacts with CYC.
 When CYC is consumed, the concentration
of Br2 suddenly rises, signaling the end of
the titration.

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Coulometric titration (const. current), cont.:
 The rise in Br2 concentration is detected by measuring the current between two Pt detector
electrodes (in the detection circuit). A voltage of 0.25 V applied between these two electrodes is
not enough to electrolyze any solute, so only a tiny current of <1 A flows through the
microammeter.
 At the equivalence point, CYC is consumed, [Br2] suddenly increases and the detector current flows
as a result of the reaction: - -
Detector cathode: Br2 + 2e 2Br
Detector anode: 2Br- Br2 + 2e-
 Note that both Br2 and Br- must be present for the detector half-reactions to occur.

 In coulometric titration, the time needed to generate (at constant current) equivalent amount of Br 2
to the analyte is measured.
Applications and Advantages of coulometry
1. Fully automated coulometers commonly generate H+, OH-, Ag+ and I2 to titrate a variety of analytes
including CO2, sulfides in food and sea water as well as H2O in proteins and purified solvents.

2. Unstable titrants that can not be stored or standardized such as Ag2+, Cu+, Mn3+ and Ti3+ can be
generated and used immediately in titration.

3. Toxic titrants (Br2) that can not be used safely in conventional titration methods can be generated
and consumed as soon they are formed in coulometric vessel.
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 V. How to quantify in coulometry
Faraday’s law: The amount of chemical reaction at an electrode (e.g., mass
of copper deposited on the cathode surface) is proportional
to the quantity of electricity passed in the circuit.

Faradaic current: Current that passes in the circuit as a result of actual

electrolysis (oxidation and reduction at electrode surface).

q  I . t
Coulombs Amperes seconds
I.t
Moles of e  
F
If a reaction requires n electrons per mole of reactant, the quantity reacting of chemical species
in time t is
I.t
Moles reacted 
n F
I.t
Mass  . ( molar mass) Faraday’s Law
n F
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 References
1. “Principles of instrumental analysis, 5th ed. by Skoog, Holler,
Nieman” Chapter 22 and Chapter 24.
2. “Quantitative Chemical Analysis, 6th ed. Daniel Harris”
Chapter 17.
3. Lecture of “Non- potentiometric methods of analysis ” by Dr.
Raafat Aly, GUC, spring 2010.

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