Application Area: Fundamental

Ohmic Drop
Part 1 – Basic Principles

Keywords the composition of the electrolyte give rise to the equipotential

lines, i.e., regions of the electrode-electrolyte interface where
Uncompensated resistance; Ohmic drop determination;
the potential between RE and WE has the same value.
Ohmic drop compensation

Summary
A typical electrochemical experiment is performed using a RE1 RE2 RE3
three electrode setup; a working electrode (WE), a counter or
auxiliary electrode (CE), and a reference electrode (RE). In
addition, a sense (S) lead is connected to the WE. Therefore,
the potential applied to the cell is controlled by applying
current between the CE and WE, and measuring the potential
between the RE and S. In order to have reliable
measurements of the potential, the reference electrode WE
should ideally be non-polarizable.
When current is flowing through an electrochemical cell, a
potential drop between the RE and the WE will occur. This
voltage drop is influenced by the electrolyte conductivity, the
distance between the reference and the working electrodes,
and the magnitude of the current.
Using Ohm’s law, the ohmic (voltage) drop ∆𝐸 can be
calculated to be equal to the product of the current 𝑖 and the
ohmic or uncompensated resistance 𝑅 :
Equipotential
lines
∆𝐸 = 𝑖𝑅 1
Figure 1 – Equipotential lines shown at close proximity to the
working electrode.
Assuming that the passage of current does not affect the
potential of the reference electrode (ideally non-polarizable),
Consequently, the ohmic drop value depends on the following
the measured potential of the working electrode is given by
factors:
the equation:

1. The current and potential distribution in the electrolyte,

𝐸 =𝐸 − ∆𝐸 =𝐸 − 𝑖𝑅 2
which in turn depends on the geometry of the
experimental cell. Therefore, changing the size or shape
Factors affecting the ohmic drop of the WE will change the shape of the equipotential
lines.
Consider the potential profile in Figure 1, at the working
2. The position of the RE with respect to the WE. If the RE
electrode – electrolyte interface.
is placed exactly at the electrode surface, then the ohmic
The CE is placed relatively far and it is assumed not to
drop is zero (RE1). As the RE is moved away from the
influence the current and potential distribution. RE1, RE2 and
WE (RE2 and RE3), the ohmic resistance, and therefore
RE3 are examples of the various positions where the
the ohmic drop between WE and RE increases.
reference electrode RE can be placed to measure the
3. The conductivity of the electrolyte solution. The lower the
potential vs. the WE. The geometry of the WE surface and
conductivity of the electrolyte, the higher the ohmic
 Application Area: Fundamental
Ohmic Drop
Part 1 – Basic Principles

resistance and therefore the ohmic drop. Conductivity is scan rates, i.e., when 𝑡 is much bigger than 𝑅 𝐶 , the
in turn affected by other experimental factors, such as exponential approaches 0 and the errors can be negligible.
the temperature of the system.

Cell design and electrode placement

Impact of the ohmic drop on measurements From Equation 3, it can be seen that for fast experiments, the
The ohmic drop can have significant impact in fast time constant 𝑅 𝐶 has a significant influence on the errors
experiments, experiments with high currents, or those that in the true potential at the electrode surface. Even for slow
require long-term passage of currents, like during experiments, high ohmic resistance can lead to incorrect or
electrolysis. Also experiments carried out in low conductivity misleading results.
media, such as in concrete or organic electrolyte, can be These errors can be minimized by reducing either 𝑅 or 𝐶 .
strongly affected by the ohmic drop. This can be achieved by
Under potentiostatic control, there is always a potential drop
due to the ohmic resistance Equation 2. Therefore,
1. Increasing the conductivity of the solution by using a
depending on the sign of the current, the measured potential
supporting electrolyte. The conductivity is inversely
will be less negative or more positive than the potential if
proportional to the resistivity and therefore to 𝑅 .
there would be no 𝑖𝑅 drop, called nominal potential. If
2. Decreasing the size of the working electrode, to
cathodic (negative) currents flow, the measured potential will
decrease 𝐶 . The area of a capacitor is directly
be less negative than the nominal potential. If anodic,
proportional to its capacitance.
therefore positive currents flow, the measured potential will
3. Moving RE as close as possible to WE, in order to
be less positive than the nominal potential.
reduce 𝑅 . This is often done by using a very fine
When large currents are employed, even small ohmic capillary tip, called Luggin-Haber or Luggin capillary,
resistance values can cause large errors. For example, if the along with RE. It must be remarked that it is not possible
ohmic resistance is 1  and the current is 1 A, the error due to place RE in contact with the WE surface, since the
to ohmic drop is 1 V. This is one of the reasons why industrial measured potential would be zero!
electrosynthesis are usually carried out under galvanostatic
control, where the potential between RE and WE is only
measured, but not controlled, therefore no 𝑖𝑅 drop is Note: care must be taken when using a Luggin capillary
present. because it can cause shielding errors. Shielding can appear
when the surface of WE is blocked by RE, which can occur if
For low-conductivity media such as electrolytes with low salt
they are too close to each other. This can cause non-uniform
concentration organic electrolytes, or concrete, the ohmic
current distribution at the electrode surface. If a Luggin
resistance can be very high, on the order of several k
capillary with a tip diameter 𝑑 is used, the closest distance it
Therefore, even small currents can lead to large errors in
can be placed without causing appreciable shielding error is
potential. For example if the ohmic resistance is 10 k and
2𝑑 from the WE. Therefore, even when the tip of the RE is
the current is 100 µA, the error is 1V.
designed for very close placement to the WE, with a Luggin
In a fast experiment (cyclic voltammetry with a fast scan) capillary, some uncompensated potential drop usually
there is a current transient due to the charging and remains.
discharging of the double layer.
At distances very close to the WE, the equipotential lines are
Therefore, when the potential is scanned the measured close together and small variations in the position of the RE
potential lags the applied potential according to the following can lead to large variations in the ohmic drop. In some cases,
equation: it is preferable not to use a Luggin capillary but to place the
reference electrode far from the working electrode and
measure and compensate for the ohmic drop, as explained in
𝐸 =𝐸 1−𝑒 3
a separate application note.

Where 𝑅 is the ohmic resistance, 𝐶 is the double layer

capacitance and t is the time at which the measurement is
taken. For fast scan rates, i.e., when 𝑡 is much smaller
than 𝑅 𝐶 , the exponential approaches 1 and significant
errors in 𝐸 with respect to 𝐸 can arise. For slow

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 Application Area: Fundamental
Ohmic Drop
Part 1 – Basic Principles

Date
March 2019 AN-EC-003

For more information

Additional information about this application note and the
associated NOVA software procedure is available from your
local Metrohm distributor. Additional instrument
specification information can be found at
www.metrohm.com/en/products/electrochemistry.

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