Coulometry

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 Outline
Introduction
Principle of coulometry
Apparatus and measurement of coulometry
Applications of coulometric methods

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 Objective
At the end of the session the student shall be able to
describe:
Principle of coulometry
Apparatus and measurement of coulometry
Applications of coulometric methods

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 Introduction
Coulometric methods are based upon stoichiometrical
relationships (quantitative conversion of the analytes).
The concentration of an analyte is calculated from the
quantity of electricity, using the equation Q=It.
Standardization or calibration curves are not required.
This is not therefore a comparative method.
Two types of coulometric methods co-exist:
A) Potentiostatic coulometry
B) Coulometric titration or amperostatic coulometry

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  Coulometry determines the amount of matter transformed
during an electrolysis reaction by measuring the amount of
electricity (in coulombs) consumed or produced.
 It can be used for precision measurements of charge, and the
amperes even used to have a coulometric definition.
 However, today coulometry is mainly used for analytical
applications.
 Coulometry is a group of techniques in analytical chemistry.
 It is named after Charles-Augustin de Coulomb.
 The other, called coulometric titration or amperostatic
coulometry, keeps the current (measured in amperes) constant
using an amperostat.

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 Coulometry is based on an exhaustive electrolysis of
the analyte.
By exhaustive we mean that the analyte is completely
oxidized or reduced at the working electrode or that it
reacts completely with a reagent generated at the
working electrode.
There are two forms of coulometry: controlled-
potential coulometry, in which we apply a constant
potential to the electrochemical cell, and controlled-
current coulometry, in which we pass a constant
current through the electrochemical cell.
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 During an electrolysis, the total charge, , in coulombs,
passing through the electrochemical cell is
proportional to the absolute amount of analyte by
Faraday’s law

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 Potentiostatic coulometry
 Potentiostatic coulometry is a technique most commonly referred to
as "bulk electrolysis".
 The working electrode is kept at a constant potential and the current
that flows through the circuit is measured.
 This constant potential is applied long enough to fully reduce or
oxidize all of the electroactive species in a given solution.
 As the electroactive molecules are consumed, the current also
decreases, approaching zero when the conversion is complete.
 The sample mass, molecular mass, number of electrons in the
electrode reaction, and number of electrons passed during the
experiment are all related by Faraday's laws.
 It follows that, if three of the values are known, then the fourth can
be calculated

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  Bulk electrolysis is often used to unambiguously assign the
number of electrons consumed in a reaction observed
through voltammetry.
 It also has the added benefit of producing a solution of a
species (oxidation state) which may not be accessible
through chemical routes.
 This species can then be isolated or further characterized
while in solution.
 The rate of such reactions is not determined by the
concentration of the solution, but rather the mass transfer
of the electroactive species in the solution to the electrode
surface.
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 Rates will increase when the volume of the solution is
decreased, the solution is stirred more rapidly, or the
area of the working electrode is increased.
Since mass transfer is so important the solution is
stirred during a bulk electrolysis.
 However, this technique is generally not considered a
hydrodynamic technique, since a laminar flow of
solution against the electrode is neither the objective
nor outcome of the stirring.

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 The extent to which a reaction goes to completion is
also related to how much greater than the applied
potential the reduction potential of interest.

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 Coulometric titration
 Coulometric titrations use a constant current system to accurately
quantify the concentration of a species.
 In this experiment, the applied current is equivalent to a titrant.
 Current is applied to the unknown solution until all of the
unknown species is either oxidized or reduced to a new state, at
which point the potential of the working electrode shifts
dramatically.
 This potential shift indicates the endpoint.
 The magnitude of the current (in amperes) and the duration of the
current (seconds) can be used to determine the moles of the
unknown species in solution.
 When the volume of the solution is known, then the molarity of
the unknown species can be determined
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 Advantages of Coulometric Titration
 Coulometric titration has the advantage that constant current sources for
the generation of titrants are relatively easy to make.
 The electrochemical generation of a titrant is much more sensitive and can be
much more accurately controlled than the mechanical addition of titrant using
a burette drive.
 For example, a constant current flow of 10 µA for 100ms is easily generated and
corresponds to about 10 micrograms of titrant.
 The preparation of standard solutions and titer determination is of course no
longer necessary.
 Chemical substances that are unstable or difficult to handle because of their
high volatility or reactivity in solution can also very easily be used as titrants.
 Examples are bromine, chlorine, S, , S, and Karl Fischer reagents (iodine).
 Coulometric titration can also be performed under inert atmosphere or be
remotely controlled e.g. with radioactive substances.

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 Apparatus and measurement
 The easiest way to ensure 100% current efficiency is to hold the
working electrode at a constant potential, chosen so that the
analyte reacts completely without simultaneously oxidizing or
reducing an interfering species.
 As electrolysis progresses the analyte’s concentration decreases,
as does the current.
 The resulting current-versus-time profile for controlled-potential
coulometry is shown in Figure 1.
 Integrating the area under the curve (equation) from t = 0 to t =
gives the total charge.
 In this section we consider the experimental parameters and
instrumentation needed to develop a controlled-potential
coulometric method of analysis.
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 Cont’d…

Figure 1 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.

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 Selecting a Constant Potential
To see how an appropriate potential for the working
electrode is selected, let’s develop a constant-potential
coulometric method for Cu based on its reduction to
copper metal at a Pt working electrode.

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 To ensure a 100% current efficiency, however, the
potential must be sufficiently more positive than
+0.000 V so that the reduction of to does not
contribute significantly to the total current flowing
through the electrochemical cell.

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 Figure 2: Ladder diagram for an aqueous solution of
showing steps for the reductions of to O, of to Cu, and
to . For each step, the oxidized species is in blue and the
reduced species is in red

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 Controlled-Current Coulometry
 A second approach to coulometry is to use a constant current in
place of a constant potential, which produces the current-versus-
time profile shown in Figure 3.
 Controlled-current coulometry has two advantages over
controlled-potential coulometry.
 First, the analysis time is shorter because the current does not
decrease over time.
 A typical analysis time for controlled-current coulometry is less
than 10 min, compared to approximately 30–60 min for
controlled-potential coulometry.
 Second, because the total charge is simply the product of current
and time (equation), there is no need to integrate the current-time
curve in Y.
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 Figure 3: Current versus time for a controlled-current coulometric
analysis.
The measured current is shown by the red curve.
The integrated area under the curve, shown in blue, is the total
charge.
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 Maintaining Current Efficiency

Figure 4: shows the ladder diagram for this system.

At the beginning, the potential of the working electrode
remains nearly constant at a level near its initial value.
As the concentration of Fe decreases, the working
electrode’s potential shifts toward more positive values
until the oxidation of begins.
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 Because a portion of the total current comes from the
oxidation of the current efficiency for the analysis is less
than 100%

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 Figure 4: Ladder diagram for the constant-current coulometric analysis of Fe .
The red arrow and text shows how the potential drifts to more positive values,
decreasing the current efficiency.

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 Applications of coulometric methods
 Karl Fischer reaction
 The Karl Fischer reaction uses a coulometric titration to determine the
amount of water in a sample.
 It can determine concentrations of water on the order of milligrams per
liter.
 It is used to find the amount of water in substances such as butter,
sugar, cheese, paper, and petroleum.
 The reaction involves converting solid iodine into hydrogen iodide in
the presence of sulfur dioxide and water.
 Methanol is most often used as the solvent, but ethylene glycol and
diethylene glycol also work.
 Pyridine is often used to prevent the buildup of sulfuric acid, although
the use of imidazole and diethanolamine for this role are becoming
more common.
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 All reagents must be anhydrous for the analysis to be
quantitative. The balanced chemical equation, using
methanol and pyridine, is:

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 Cont’d…
 On the above reaction, a single molecule of water reacts
with a molecule of iodine.
 Since this technique is used to determine the water content
of samples, atmospheric humidity could alter the results.
 Therefore, the system is usually isolated with drying tubes
or placed in an inert gas container.
 In addition, the solvent will undoubtedly have some water
in it so the solvent’s water content must be measured to
compensate for this inaccuracy.

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  To determine the amount of water in the sample, analysis must first be
performed using either back or direct titration.
 In the direct method, just enough of the reagents will be added to
completely use up all of the water.
 At this point in the titration, the current approaches zero.
 It is then possible to relate the amount of reagents used to the amount of
water in the system via stoichiometry.
 The back-titration method is similar, but involves the addition of an excess
of the reagent.
 This excess is then consumed by adding a known amount of a standard
solution with known water content.
 The result reflects the water content of the sample and the standard solution.
 Since the amount of water in the standard solution is known, the difference
reflects the water content of the sample.

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 Determination of film thickness

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  The electrodes for this reaction are often platinum electrode
and an electrode that relates to the reaction.
 For tin coating on a copper wire, a tin electrode is used,
while a sodium chloride-zinc sulfate electrode would be
used to determine the zinc film on a piece of steel.
 Special cells have been created to adhere to the surface of
the metal to measure its thickness.
 These are basically columns with the internal electrodes
with magnets or weights to attach to the surface.
 The results obtained by this coulometric method are similar
to those achieved by other chemical and metallurgic
techniques.
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 THANK YOU

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