Electrogravimetry and Coulometry

Lecture 1

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Electrogravimetry and Coulometry
Three electroanalytical methods are based on
electrolytic oxidation or reduction of an analyte for a
sufficient period of time, to assure its quantitative
conversion to a new oxidation state. These methods
are constant-potential coulometry; constant-current
coulometry (or coulometric titrations), and
electrogravimetry. In electrogravimetric methods, the
product of the electrolysis is weighed as a deposit on
one of the electrodes.
In the two coulometric procedures, on the other hand,
the quantity of electricity needed to complete the
electrolysis is a measure of the amount of analyte
present.
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These three methods generally have:
1. moderate selectivity, sensitivity, and speed
2. In many instances, they are among the most accurate
and precise methods available, with uncertainties of a
few tenths of a percent RSD being common.
3. Finally, these three techniques require no calibration
standards; that is, the relationship between the quantity
measured and the mass of analyte, or electrical charge
passed, can be calculated from theory.

Applications of electrogravimetric methods will be discussed

only briefly, as the topic is rather familiar and simple.
Before starting a detailed discussion, we explore the
processes that occur in an electrolytic deposition.

3
 Units for Quantity of Electricity
The quantity of electricity, or charge, is measured
in units of coulombs (C). A coulomb is the
quantity of charge transported in one second by
a constant current of one ampere. Thus, for a
constant current of I amperes for t seconds, the
charge in coulombs Q is given by the expression:
Q = It
For a variable current i, the charge is given by the
Integral:
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5
The faraday F is the charge in coulombs of one mole of
electrons. The charge of the electron is 1.60218*10-19 C, so
we may therefore write:

6.02214 ∗ 1023 𝑒 1.60218 ∗ 10−19 𝐶

𝐹= ∗ = 96485 𝐶 𝑚𝑜𝑙 𝑒
𝑚𝑜𝑙 𝑒 𝑒

Faraday's law relates the number of moles of the analyte nA to

the charge
𝑄
𝑛𝐴 =
𝑛𝐹
where n is the number of moles of electrons in the analyte half-
reaction.
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 CURRENT-VOLTAGE RELATIONSHIPS
DURING AN ELECTROLYSIS
An electrolysis can be performed in one of three ways:
(1) Using a constant applied cell voltage,
(2) Using a constant working electrode potential, or
(3) Using a constant electrolysis current passing through
the cell.
It is useful to consider the consequences of each of
these modes of operation. For all three modes, the
behavior of the cell is governed by the equation:
Eappl = Ec – Ea – IR + (Pcc + Pck) + (Pac + Pak)

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where Eappl is the applied voltage from an external
source and Ec , and Ea , are the reversible, or
thermodynamic, potentials associated with the right-
and left-hand electrodes, respectively. The term P
represents overvoltages resulting from concentration
and kinetic polarization at both electrodes.
The values for Ec , and Ea , can be calculated from
standard potentials using the Nernst equation. In
many cases, only the working electrode is polarizable
because the other electrode is a non-polarizable
reference electrode. The overvoltage, P, is the extra
voltage, above the thermodynamic potential,
required to drive the electrode reaction at a certain
rate, and thus produce the required current in the
cell.

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 Methods Based on Electrogravimetry
We have three modes of electrolysis:
1. Constant Cell Potential Electrolysis
2. Constant Working Electrode Potential
Electrolysis
3. Constant Current Electrolysis

We will study all three techniques.

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1. Operation of the Cell at a Constant
Applied Potential
The simplest way of performing an analytical electrolysis is to
maintain the applied cell potential at a constant value. In practice,
electrolysis at a constant cell potential is limited to the separation
of easily reduced cations from those that are more difficult to
reduce than hydrogen ion. In the cell below, the cathode is a
platinum electrode, with a surface area of 150 cm2 immersed in
200 mL of a solution that is 0.0220 M in copper(II) Ion and 1.00 M
in hydrogen ion. When a suitable potential difference is applied
(to be determined later) between the two electrodes, copper is
deposited on the cathode, and oxygen is evolved at a partial
pressure of 1.00 atm at the anode.
Cu2+ + H2O g Cu(s) + ½ O2(g) + 2H+
The analyte here is copper(Il) ions in a solution containing an excess
of nitric acid.

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11
 Calculation of the Required Cell Potential
Standard potential data for the two half-reactions in the cell
under consideration are:
Cu2+ +2e g Cu(s) EO = 0.337 V
½ O2(g) + 2H+ + 2e g H20 EO = 1.23 V
Cu2+ + H2O → Cu(s) + ½ O2(g) + 2H+ EO = -0.94 V
The thermodynamic potential for this cell can be shown to
be -0.94 V (since Cu2+ needs to be deposited).
Ecell = Ec – Ea = 0.34 – 1.23 = -0.94 V
Thus, we expect no current at applied potentials less
negative than -0.94V. At just greater negative potentials, a
linear increase in current with potential should be
observed in absence of kinetic or concentration
polarization. However, usually a much larger potential is
needed to force high current passage (mainly due to
concentration polarization), and thus reduce time
required for electrodeposition.
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13
assume that we wish to operate the cell initially at a current
of 1.5A, which corresponds to a 0.010A/cm2 current
density (for a 150 cm2 cathode):
→ in the literature it is found that the oxygen overvoltage
(at the anode), will be about -0.85V
→ concentration polarization will be negligible at the
beginning (at the cathode)
→ because the concentration of copper ions is initially high
(0.022 M, this means an electrode potential of 0.29 V)
→ assuming a solution resistance of 0.05 Ohms
Eappl = Ec – Ea + (Pcc + Pck) + (Pa) – IR
Eappl = 0.29 - 1.23 + 0 + (-0.85) - 0.050 x 1.5 = -2.54V
* thus, a rough estimate of the potential required to produce
an initial current of 1.5A is -2.5V

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15
 Current Changes during an Electrolysis
at Constant Applied Potential
It is useful to consider the changes in current in the cell under
discussion when the potential is held constant at - 2.5 V
throughout the electrolysis. Under these conditions, the
current decreases with time as a result of the depletion of
copper ions in the solution, as well as the increase in
cathodic concentration polarization. In fact, with the onset
of concentration polarization, the current decrease becomes
exponential in time. That is:
It = Io*e-kt and k = 25.8 D*A/Vd
where It , is the current at time t in min, after the onset of
polarization and Io is the initial current.

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D: the diffusion coefficient(cm2/s), or the rate at
which the reactant diffuses under a unit
concentration gradient,
A: the electrode surface area(cm2),
V: the volume of the solution (cm3), and
δ: the thickness of the diffusion layer in which the
concentration gradient exists
Typical values for D and δ are 10-5 cm2/s and 2 × 10-3
cm
The constant 25.8 includes the factor of 60 for
converting D to cm2/min, thus making k
compatible with the units of t in the equation for
It

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 (a) Current; (b) IR drop and cathode potential change during
electrolytic deposition of copper at a constant applied cell potential.
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When the initial applied potential is - 2.5 V, we
find that concentration polarization, and thus
an exponential decrease in current occurs
essentially immediately after applying the
potential. The previous figure depicts this
behavior; the data for the curve shown were
computed for the cell using the preceding
equation. After 30 min, the current decreases
from the initial 1.5 A to 0.08 A. By this time,
approximately 96% of the copper has been
deposited.

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 Potential changes During an Electrolysis at
Constant Applied Potential
1. The thermodynamic anode potential remains
substantially unchanged throughout the electrolysis
because of the large excess of the reactant (water) and
the small change in the concentration of reaction
product (H+).
2. The calculated reversible cathode potential (the dashed
line), Ec, becomes smaller (more negative) as the copper
concentration decreases.
3. The IR drop shown in figure parallels the changes in
current with time.
4. The shift in cathode potential that accompanies
concentration polarization often leads to codeposition of
other species and loss of selectivity

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 IR drop and cathode potential change during electrolytic deposition of
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copper at a constant applied cell potential.
the IR drop decreases continually as the reaction proceeds,
since the current continues to decrease, due to decreased
mass transport to electrode surface. The reason for this
decrease is primarily concentration polarization at the
cathode, which limits the rate at which copper ions are
brought to the electrode surface and thus the current
decreases. As shown in the previous figure, the decrease
in IR must be offset by an increase in the cathode
potential (more negative) because the applied cell
potential is constant.

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It should be noted that co-deposition of hydrogen
during electrolysis often leads to formation of non-
adherent deposits, which are unsatisfactory for
analytical purposes. This problem can be resolved by
introducing another species that is reduced at a less-
negative potential than hydrogen ion and does not
adversely affect the physical properties of the
deposit. One such cathode depolarizer is nitrate ion.
Hydrazine and hydroxylamine are also commonly
used.
Consider a case in which a solution contains Cu2+ and
Pb2+ ions. Lead (II) begins to deposit at point A on the
cathode potential curve. Hence lead (II) ions would
co-deposit well before copper deposition (at point D)
was complete and would interfere.
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The decrease in current and the increase in cathode
potential is slowed at point B by the reduction of
hydrogen ions. Because the solution contains a large
excess of acid, the current is now no longer limited by
concentration polarization of copper ions, and co-
deposition of copper and hydrogen ions occurs
simultaneously until the remainder of the copper ions is
deposited. Under these conditions, the cathode is said to
be depolarized by hydrogen ions.

Note that as the cathode potential becomes more negative,

metals that are reduced at potentials less than B will co-
deposit with the analyte.
However, metals that are reduced at point C will not co-
deposit because of the almost constant non-increasing
potential (solid line), as a result of reduction of H+, which
has a high concentration.
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 The cathodic depolarizer, nitrate
ion, gets reduced at a potential
less negative than at point B
(thus preventing hydrogen
evolution):
NO3- + 10H+ + 8e D NH4+ + 3H2O

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Co-deposition of hydrogen during electrolysis often
leads to spongy and flaky deposits that do not
adhere to the electrode. Such a situation is
unsatisfactory for analytical purposes. The use of
depolarizers often improves the efficiency of the
process. A depolarizer is a substance which gets
reduced at the cathode without gasification or gets
oxidized at the anode before oxygen evolution and
stabilizes the potential of the working electrode by
minimizing concentration polarization. Thus copper
deposited from a nitric acid solution is smoother
and more adherent because nitrate ions act as
cathodic depolarizers and prevent evolution of
hydrogen. Generally reducing agents like hydrazine
hydrochloride will act as anodic depolarizers.

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Consider now the fate of some metal ions, such as lead(Il),
that begins to deposit at point A on the cathode potential
curve. Lead(II) would co-deposit well before copper
deposition was complete and would therefore interfere
with the determination of copper. In contrast, a metal ion
that reacts at a cathode potential corresponding to point C
on the curve would not interfere because depolarization
by hydrogen gas formation prevents the cathode from
reaching this potential. At best, an electrolysis at constant
potential can be used only to separate easily reduced
cations, such as Pb(II), Cd(II), Ag(I), TI(I), Cu(II), and Zn(II),
from those that are more difficult to reduce than
hydrogen ion, such as AI(III). Therefore, hydrogen
evolution occurs near the end of the electrolysis and
prevents interference by cations that are reduced at more
negative potentials.

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 2. Electrolysis at Constant Working
Electrode Potentials
From the Nernst equation, we see that a tenfold
decrease in the concentration of an ion being
deposited requires a negative shift in potential of only
0.0592/n V.
Electrolytic methods, therefore, are reasonably
selective. For example, as the copper concentration of
a solution is decreased from 0.10 M to 10-6 M, the
thermodynamic cathode potential E, changes from an
initial value of +0.31 to +0.16 V (values are derived
from Nernst equation). In theory, then, it should be
feasible to separate copper from any element that
does not deposit within this 0.15V potential range.

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Species that deposit quantitatively at potentials more
positive than +0.31 V could be eliminated with a
prereduction step, (by adjusting the potential at less
positive potential than +0.31 V); ions that require
potentials more negative potentials than +0.16 V
would not interfere with the copper deposition. Thus,
if we are willing to accept a reduction in analyte
concentration to 10-6 M as a quantitative separation,
it follows that divalent ions differing in standard
potentials by about 0.15 V or greater can,
theoretically, be separated quantitatively by
electrodeposition, provided their initial
concentrations are about the same. Correspondingly,
about 0.30 and 0.10V differences are required for
univalent and trivalent ions, respectively.

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Separations with Controlled electrode Potential
Electrolysis
An approximate value of the limiting potential of the working
electrode for a specific electrogravimetric process can be
calculated from the Nernst equation, but lack of knowledge
concerning the overpotential term(s) for a system severely limits
its usefulness. A more reliable method utilizes the overpotential
information obtained from current–potential curves at solid
electrodes.
Example:
What range of cathode potentials is needed to deposit silver
quantitatively (that is, to lower the silver concentration to at least
10−6 M) from a solution 0.0100 M in silver nitrate?
Ag+ + e D Ag(s) Eo = 0.790 V
Deposition of silver will commence when the cathode potential is:
E = 0.790 + 0.0592 log 0.01 = 0.672 V

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The removal of silver ions would be considered
complete at:
E = 0.790 + 0.0592 log 10-6 = 0.435 V

Thus, the deposition would begin at 0.672 V and

would be completed at 0.435 V, a difference of
0.237 V.
When a saturated calomel electrode (0.242 V
versus the standard hydrogen electrode) is used
as the auxiliary reference electrode, the range
would be from 0.430 to 0.193 V

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Would the silver removal be complete before the copper
would commence to plate from a solution that is 0.010M
in copper(II) ions?
Copper(II) ions would commence to deposit at:
E = 0.337 + {0.0592/2} log 10-2 = 0.278 V (0.036 vs SCE)
The removal of silver would be complete at 0.193 V (versus
SCE), whereas copper would start to deposit at 0.036 V
versus SCE.
Controlling the cathode potential somewhere in the interval
between 0.2 and 0.05 V versus SCE should be satisfactory.
The current through the system steadily decreases as the
deposition proceeds. However, the maximum permissible
current is used at all times so the electrolysis proceeds at
the maximum rate.

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Consider the quantitative removal of cadmium from a
solution 0.0100M in cadmium ions, using a platinum
electrode (the hydrogen overpotential over platinum is
about 0.09 V) in a 0.1 M nitric acid solution. To what pH
must the solution be adjusted in order to prevent
interference from the evolution of hydrogen gas?
In a 0.1M nitric acid solution, hydrogen would commence to
evolve at a platinum electrode when:
E = 0.000 + {0.0592/1} log 10-1 = - 0.0592 V
However, cadmium would not commence plating until:
E = -0.403 + {0.0592/2} log 10-2 = - 0.444 V
The separation is impossible at pH 1 with use of platinum
electrodes since hydrogen will evolve at -0.0592 V, a much
lower negative potential than cadmium starting
deposition potential, and therefore it interferes.

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However, two changes in the procedure will enable cadmium
to be deposited at this pH.
1. Using an acetate buffer and adjusting the pH of the
solution to pH 5 will shift the electrode potential at
which hydrogen evolves to a more negative value.
E =0.000 + {0.0592/1} log 10-5= -0.296V
This is not enough to exclude interference of H+
2. Second, use an electrode that has been pre-coated with
copper because the hydrogen overpotential is about 0.4
V on copper. This means that hydrogen will not evolve at
potentials less negative than -0.696 V on this copper
coated electrode. Therefore, hydrogen will not interfere
until the cathode potential reaches about −0.7 V. At this
potential,
-0.7 = -0.403 + {0.0592/2} log [Cd2+]
[Cd2+] < 1.4*10-10 M
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Is a quantitative separation of Cu2+ and Pb2+ by
electrolytic deposition feasible in principle? If so,
what range of cathode potentials versus the saturated
calomel electrode (SCE) can be used? Assume that the
sample solution is initially 0.1000 M in each ion and
that quantitative removal of an ion is realized when
only 1 part in 10,000 remains undeposited.
Cu2+ +2e D Cu(s) Eo = 0.337 V
Pb2+ +2e D Pb(s) Eo = -0.126 V
Note that based on the standard potentials, copper will
begin to deposit at more positive applied voltages
than lead. Let us first calculate the potential required
to reduce the Cu2+ concentration to 10-4 of its original
concentration (that is, from 0.1000 M to 1.00*10-5 M).

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36
 Large Versus Small Currents
Concentration polarization and overvoltage may prevent
application of theoretically deduced potential
differences for separations. This is mainly due to the
fact that the change in cathode potential is governed
by the decrease in IR drop (due to decrease in current
with time).
Thus, for instances in which relatively large currents are
applied initially, the change in cathode potential can
ultimately be expected to be large. On the other
hand, if the cell is operated at low current levels so
that the variation in cathode potential is decreased,
the time required for completion of the deposition
may become prohibitively long.
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 Apparatus for controlled-
potential, or
potentiostatic,
electrolysis. Contact C is
adjusted as necessary to
maintain the working
electrode (cathode in this
example) at a constant
potential. The current in
the reference electrode is
essentially zero at all
times. Modern
potentiostats are fully
automatic and frequently
computer controlled.
The electrode notations
in the figure are the
currently acceptable
notations.
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