Guidance Note

Performing Current Step Measurements

Introduction
This guidance note describes the process of determining a polarization curve using a
current step method (i.e. applying a series of fixed currents). This method requires the
minimum amount of equipment, but is a little tedious to perform, and has some
limitations, especially for systems exhibiting an active-passive transition. You will
need the following equipment (in addition to the electrodes, cell and solution that will
be specific to your experiment):

1.5 V and 9 or 12 V batteries

Selection of resistors
Voltmeter

We are going to apply a current using a battery together with a resistor to limit the
current. This does not give a truly constant current, as the current will be influenced
by the cell voltage, but we are going to measure the current as a part of the
measurement process, so this does not lead to errors in the measurement.
If we ignore the voltage across the cell, the current will be given by the battery
voltage divided by the value of the resistor. Since the current typically varies over a
wide range, we shall need a wide range of resistor values to give a suitable range of
current. For a 0.2 mm diameter copper electrode with length of about 4 cm, the
maximum current required is in the region of 10 mA. The cell voltage at this high
current will be in the region of 4 V, so with a 9 V battery we shall need a resistor of 5
V/0.01 A or 500 the closest standard value to this is 470 . Well also use a 1.5 V
battery for the lower currents, since it is difficult to get very large value resistors in
order to obtain small currents. Then the ideal selection of resistors will increase in a
geometric sequence. With three resistors per decade this gives something like 470, 1k,
2.2k, 4.7k, 10k, 22k, 47k, 100k, 220k, 470k, 1M, 2.2M, 4.7M, 10M. The power
dissipation in the resistor is a maximum for the smallest resistor value (it is given by
V2/R); with 9 V applied to 470 the dissipation will be less than 0.25 W, so 0.25 W
resistors will be suitable, and should be available very cheaply. Ask the lab technician,
and he will provide resistors to your group. You will also need some wiring, crocodile
clips and battery connectors, which you can also get from RSH (if you chose to order
from them we have prepared a list of parts please note that this is not an
endorsement of this company, we have never used them, they just happened to come
up when we looked on the Internet).

Procedure
A simple method of using a battery plus resistors to apply a current to a cell is to use
two identical working electrodes, one of which is polarized as an anode, and the other
as a cathode. This way we can construct both the anodic and cathodic curves at the
same time. Note that it is normal to step from a more negative potential to a more
positive one, as this means that the damage caused by anodic dissolution of the
sample occurs towards the end of the test, and does not influence the results at

cathodic potentials. There may, however, be some effects due to hydrogen dissolved
in the surface layers of the sample, which can oxidise at more positive potential and
produce a false anodic current. This error is reduced as the time between steps is
increased.

Voltmeter

Battery
(9 or 1.5V)

Voltmeter

Voltmeter

WE

RE

WE

Figure 1 Cell configuration (note that this drawing uses the common
convention that lines that meet at a T junction are connected, but lines
that cross are not)

The cell configuration is then shown in Figure 1. This shows three voltmeters, and if
you have them you can use all three, but it is permissible to move one meter between
the three connections.
Place the three electrodes in the cell, making sure that they are reasonably uniformly
spaced. It is common to perform experiments under natural aeration conditions, i.e.
we allow access of oxygen, but dont deliberately aerate or stir the solution. Under
these conditions the results will be strongly affected by slight stirring of the solution,
so be careful not to disturb the cell once you have started the experiment.
First of all, measure the potential of the two working electrodes with the battery
unconnected (i.e. with no applied current). Then connect the 1.5 V battery with the
largest value resistor. Measure the voltage across the resistor (to allow the current to
be calculated) and wait for the voltage to stabilise (or for a set time), then record the
current and the potential of each of the two working electrodes relative to the
reference electrode.
Repeat this process will each of the resistors in turn until you get to the smallest
resistor value. Then use the resistor with a value ten times that of the smallest resistor,
together with the 9 V battery, and repeat the measurement process, again decreasing
the resistor value at each step this should give you a table of values similar to that
shown in Table 1 you can use this as the basis of a spreadsheet to analyse your
results.
.

Battery
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
9
9
9
9

Resistor
10E6
4.7E6
2.2E6
1E6
4.7E5
2.2E5
1E5
4.7E4
2.2E4
1E4
4.7E3
2.2E3
1E3
4.7E2
4.7E3
2.2E3
1E3
4.7E2

IR

Ec

Ea

Table 1 Example table of results (note that the current density will be the voltage
measured across the resistor, IR, divided by the resistor value and by the area of
the specimen)
Use the current density and potential data to plot a graph of potential vs current
density.
Note that the input resistance (or impedance) of the meter may be comparable to the
larger values of resistance (a common value is 10 M), and to do an accurate analysis
it is necessary to correct for the effect of meter resistance. This is quite complex,
especially if you are using a single meter that you move from one measurement to
another (as the applied current will change when the meter is connected across the
resistor to measure the current), and we do not expect you to do it for this simple
experiment (i.e. assume that the meter is ideal and does not affect the measurement).

Measuring Polarization Resistance

Measuring polarization resistance using the battery and resistor technique is
particularly simple. Essentially we just want to apply a small current to the
electrode(s) and monitor the change in potential. Thus the first few measurements in
the measurement of the full polarization curve can be used directly to analyse the
polarization resistance. However, you should be particularly aware in this case of the
possible errors due to the resistance of the meter.