Introduction

Sense leads also known as working sense leads are common for many potentiostat brands. PalmSens uses the Sense lead on all models that can supply 100 mA or more. This raises the question of why a sense lead is recommended or mandatory. This article is an introduction to the sense lead including reasons for its importance and when it is used.

Purpose of a Sense lead
The potentiostat uses the potential measured by the Sense lead to correct the IR-drop inside the working electrode lead. The sense lead measures the potential at the working electrode without any current flowing. Due to its current free state, no IR-drop occurs in the sense lead and the applied potential at the working electrode is measured.

Four or five Leads

Most of PalmSens’ instruments have cables that end in four plugs with 2 mm banana connectors. These plugs show labels and colors.

  • The red plug is the working electrode lead.
  • The blue plug is the reference electrode lead.
  • The black plug is the counter electrode lead.
  • The green plug is the ground lead.
  • The yellow plug is either a BiPot or a sense lead.

Figure 1 PalmSens sensor cable with 4 banana plugs (left) and 5 banana plugs (right).

The PalmSens3, PalmSens4, and MultiPalmSens4 are available as bipotentiostats. A bipotentiostat has two working electrodes. The fifth lead of their cables is a yellow plug, which is the lead of the second working electrode.

The EmStat3+ and the EmStat4 HR have the fifth lead as well. This is also a yellow plug or if you have an older cable a bright red plug. These plugs are stackable and are used for the sense lead also known as working sense.

Ohmic Potential Drop at High Currents

Ohm’s law is well-known (Equation 1) and usually, it is read as “To increase current flow across a resistor, I need to increase the potential proportionally.” This is correct, but so is another consequence: “When a current flows through an Ohmic resistor it will create a potential drop.”

Many electrochemists are aware of that potential drop. In most experiments and cells, the drop is negligible, but if there is a large uncompensated resistance in a cell, the potential drop can be significant. However, this should be discussed in more detail, when IR-drop compensation is discussed.

Equation 1: Ohm’s law

The same principle of an Ohmic Potential drop can be observed across the cable of a potentiostat. The cable is an Ohmic resistor, and the cell current is running through it leading to an Ohmic Potential drop. A typical PalmSens sensor cable has a resistance of 0.2 Ohm. If you are measuring a current of 1 µA, the ohmic drop is 0.2 µV. This is negligible. A current of 100 mA causes an Ohmic drop of 20 mV. The result would be that your electrode experiences 20 mV less than you expect. Depending on your experiment this could be a significant amount of potential difference.

Correction by the Current free Sense Lead

The Ohmic drop across the cable can be corrected with a sense lead. The sense lead has similar function as the reference electrode lead. It measures a potential difference, and no current is supposed to flow. Ideally no current flows, in reality a very small current is required to measure the potential.

The sense lead is connected to the working electrode. It measures the potential at the working electrode without any current flowing. Due to its current free state, no IR-drop occurs in the sense lead and the applied potential at the working electrode is measured. The potentiostat can use this information to correct the IR-drop inside the working electrode lead.

This means if the current at the working electrode times the resistance of the working electrode lead reaches a significant potential drop, a sense lead is required to compensate for the Ohmic drop.

This is also the reason most potentiostats designed by PalmSens do not have a sense lead. Most of our potentiostats support current up to 30 mA, 20 mA, or 3 mA. These currents lead to a 6 – 0.6 mV Ohmic drop inside the working electrode lead, which is not significant for most setups.

The EmStat3+ and EmStat4 HR support currents up to 100 mA and 200 mA, which result in a significant potential drop.

2, 3 and 4-Electrode Measurements

Most of PalmSens’ instruments only offer a 2- or 3-electrode setup. The EmStat4 HR is also suitable for a 4-electrode setup. To understand the purpose of the 4-electrode measurement each setup (2-, 3-, and 4-electrodes) will be discussed in this section.

2-Electrode Setup

To make a 2-electrode setup just combine the counter and the reference electrode. The counter electrode of our cables is stackable, so you can conveniently combine them. You connect the working electrode (and sense) lead to one electrode and the combined counter and reference electrode lead to the other.

Figure 2: 2-electrode setup

During a measurement in a 2-electrode setup, the potential will be applied between the two electrodes and the current will flow between the same two electrodes (see Figure 2). This means the applied potential includes the potential drop across the working electrode’s interface, the potential drop across the solution, and the potential drop across the counter electrode’s interface. Any changes at the counter electrode will influence the result. If your counter electrode is expected to be stable during the measurement due to low currents or a short duration of the measurement, you can use this setup almost equivalent to a 3-electrode setup. Otherwise, this setup is only used for applications where the full cell potential is an interesting parameter, for example, fuel cells or batteries.

3-Electrode Setup

The 3-electrode setup is the most common setup during electrochemical measurements. The working electrode (and sense) will carry current and potential in this setup as it does in the 2-electrode setup. The counter electrode will still carry the current, but the potential is controlled between the working and reference electrode (see Figure 3).

Figure 3: 3-electrode setup

This has the advantage that the potential drop across the counter electrodes interface is not included in the applied potential. Another advantage is that the reference electrode does not carry any current and will thus keep a stable potential during the measurement. This means the potential of the working electrode is more accurate.

4-Electrode Setup

In the 4-electrode setup, the working electrode is split into two electrodes: the working electrode and the sense. The potential is applied between the sense lead and the reference electrode. The current flow between the working electrode and counter electrode.

Figure 4: 4-electrode setup

This way the potential drops across the counter or working electrodes’ interfaces and thus the corresponding reactions are not contributing to this measurement. Only processes across the solution and obstacles, for example, a membrane, between the sense and the reference electrode contribute.

This setup is usually only used to research solid-state electrolytes, membranes, or liquid-liquid interfaces.

The Sense Lead of EmStat3+ and EmStat4 HR

The Sense Lead of an EmStat3+

The (Multi)EmStat3+ was the first device developed by PalmSens which included a sense lead. The sense lead is only active if the 100 mA range of the EmStat3+ is activated in PSTrace. Otherwise, the sense lead will remain inactive and does not need to be connected to anything.

Figure 5: 100 mA range selected (left) and deselected (right)

The sense lead is a stackable plug-in bright red (older cables) or yellow. You can conveniently connect the working electrode plug to the back of the sense lead. The combined working electrode and sense leads are then placed just like your regular working electrode plug.

If the sense lead is not connected, while the 100 mA was selected, the potential control will not work, because it relies on the potential measured by the sense lead.

If the sense lead is not connected, while the 100 mA was not selected, the measurement will still work, but there might be additional noise. This is just a result of an extra plug and connections in your system, which are further antennas for noise.

Because the sense lead is only used when the 100 mA is active, the EmStat3+ is not recommended for 4-electrode measurements.

The Sense Lead of an EmStat4 HR

The EmStat4 HR is the successor of the EmStat3+ and is capable of measuring or applying currents up to 200 mA. Accordingly, it is equipped with a sense lead. This applies to all products based on the EmStat4 HR, for example, the EmStat4S HR and EmStat4M HR.

The sense lead is always active and needs to be connected to your working electrode, except you are making a 4-electrode measurement.

If the sense lead is not connected, the potential control will not work, because it relies on the potential measured by the sense lead.

The sense lead ends in a yellow stackable plug, so you can conveniently connect the working electrode lead’s plug. The combined working electrode and sense leads are then placed just like your regular working electrode plug. The EmStat4 HR is suitable for 4-electrode measurements.

Discover EmStat4S HR with Sense Lead