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  Electrochemical sensors
 
The electrochemical sensor is build up of a chamber consisting of two or three electrodes and an electrolyte. A membrane, like a porous PTFE-sheet, locks up the chamber for the electrolyte to come out. Gas, however, can pass through the membrane and reach the electrodes. The electrodes are usually made of platinum or gold. On the measuring electrode an electro-chemical reaction with the gas will take place where electrons will get free and diffuse to the other electrode, the counter electrode. The current of electrodes that diffuse from one electrode to the other is proportional to the gas concentration.
Electrochemical sensor
The reference electrode is necessary to build up a constant voltage between the measuring electrode and the counter electrode. Most gases react only within a small range of the reference voltage. Electrochemical sensors are available for many gases like H2S, HCN, CO, Cl2, SO2, H2, NO and NO2.

Some typical reactions of the gas and the electrolyte:
Gas Measuring electrode Counter electrode
H2S H2S + 4 H2O —> H2SO4 + 7 H+ + 8e- O2 + 4 H + 4e- —> 2 H2O
HCN 2 HCN —>2 H + 2 CN- O2 + 2 H + 2e- —> H2O
CO CO + H2O —> CO2 + 2 H+ + 2e- O2 + 4 H + 4e- —> 2 H2O
Cl2 2 H2O —> O2 + 4 H+ + 4e- 2 H+ + Cl2 + 2e- —> 2 HCl
SO2 SO2 + 2 H2O —> H2SO4 + 2 H+ + 2e- O2 + 4 H + 4e- —> 2 H2O
H2 H2 —> 2 H+ + 2e- O2 + 4 H + 2e- —> H2O
NO NO+ 2 H2O —> HNO3+ 3 H+ + 3e- O2 + 4 H + 4e- —> 2 H2O
NO2 2 H2O —> O2 + 4 H+ + 4e- NO2 + 2 H + 2e- —> NO + H2O
Depending on the measuring gas, different catalysts, electrodes, electrolytes and reference voltages are used to get the best selectivity and avoid cross sensitivity.

Electrochemical sensors are mainly used to control the ambient air on one substance. The cross sensitivity is, in most cases, to low to use the electrochemical sensor to measure several compounds at the same time.

Electrochemical sensors for oxygen
Electrochemical sensors are often used to measure oxygen. These sensors are built up similar to galvanic cells. They have 2 electrodes from different material and an electrolyte. Usually a gold and led electrode is found in the oxygen sensor. The oxygen diffuses through a PTFE-membrane and reaches the electrodes.
Oxygen sensor
The voltage between the measuring electrode and the counter electrode is proportional to the measured gas concentration.

Electrochemical reaction:

  - Measuring electrode: 4 OH- + 2 Pb —> 2 PbO + 2 H2O + 4 e-
  - Counter electrode: O2 + 2 H2O + 4 e- —> 4OH-


There are oxygen sensors that measure the partial pressure and those that measure directly the Vol%. The GfG-sensors for oxygen measure directly the Vol%.

Vol% sensors measure the percentage of the gas in the atmosphere, which is in clean dry air 20.93 vol% oxygen. The partial pressure is defined as the pressure the gas will have if no other gas is in the mixture. The partial pressure of oxygen in clean dry air is eg at a presure of 1 atmosphere 0,2093 atm.

The concentration of the gas is independent from the absolute pressure. The partial pressure changes proportional to the absolute pressure. For clean dry air at an absolute pressure of 2 atm , the following counts:
Volume in % O2 Partial pressure of O2
20,93 Vol% 0,419 atm.
The output signal of a sensor using the partial pressure changes with the absolute pressure. The sensor has to be calibrated, if it is brought in higher or lower regions (i.e. mountains or mines). On the other hand the signal of a volume % measuring sensor is uneffected by the above named changes. The oxygen volume in % did not change.