Gas Detection Technical Note

Comparison of H2S Gas Detection Technologies

Abstract Hydrogen sulphide (H2S) has one of the most readily identifiable odours known to the petrochemical and waste water industries. The familiar rotten eggs smell is detectable to the human olfactory system at concentrations below one part per million (ppm). Hydrogen sulphide is toxic; 10 ppm (Time Weighted Average) is the maximum exposure level that someone can endure for eight hours, higher concentrations (>500ppm) can cause unconsciousness and in extreme cases death. Long term exposure to concentrations above 1 ppm can irreparably damage the sense of smell, hence the requirement for a reliable vapor detection system. This paper will discuss the merits of the two most common sensing technologies used in modern safety systems for the detection of hydrogen sulphide; Electrochemical Cell (EC) and Metal Oxide Semiconductor (MOS). This paper will further indicate how the implementation of electrochemical cell technology has advanced to the point where instruments are now commercially available that demonstrate excellent performance even in hot desert environments. Electrochemical Cell Technology
1

The configuration of an electrochemical cell can be altered depending on target gas, required device stability and cost implications. An electrochemical cell consists of the same basic structure namely a number of electrodes surrounded by an electrolyte medium. The cell is enclosed in a case with a gas permeable membrane for diffusion purposes. As diffusion occurs, an oxidation or reduction reaction occurs at the sensing electrode. Electrons are exchanged between the sensing element and gas generating a change in the potential of the sensing electrode. The counter electrode is employed to balance the reaction. The unit described above refers to a two-electrode cell. These devices are best suited to applications where the expected gas concentration is confined to a limited range. Figure 1 shows the sensing and counter electrodes connected externally via a load resistor.
Load Resistor

Anode

Electrolyte

Cathode

Capillary Entrance

Figure 1: Two-electrode cell schematic

As the concentration of target gas increases, current flows causing the counter electrode to polarise. If the gas level continues to rise the potential of the sensing electrode eventually exceeds the specific range for a reaction to occur. When a cell reaches this point the output becomes non-linear thus limiting the upper most measurable concentration. This limitation can be overcome by the use of a third electrode (Reference), with an external potentiostatic operating circuit. The sensing electrode is held at a fixed potential relative to the reference. The counter
6901 West 110th Street Minneapolis, Minnesota 55438 USA page 1 of 4 Tel: 952.941.5665 or 800.765.FIRE Fax: 952.829.8750 02-February 2000

Gas Detection Technical Note

Comparison of H2S Gas Detection Technologies
electrode is still free to polarise but no longer has any effect on the sensing electrode thus allowing the cell to detect vapours over a much greater concentration range. The configuration of such a cell is given in Figure 2.
Capillary Diffusion Barrier O-ring Seal Sensing Electrode Membrane Reference Electrode Electrolyte Counter Electrode

Figure 2: Three-electrode cell schematic

Electrochemical sensors offer high sensitivity and good selectivity to the target gas. The cell provides a direct current output proportional to the gas concentration. Electrochemical cells can be described as air batteries which consume very little power, making them ideal for use in portable instruments and intrinsically-safe fixed gas detection systems. The chemical reaction of an electrochemical cell to hydrogen sulphide is given below: H2S + 2O2 H2SO4

The individual electrode reactions are given as: Sensing Electrode H2S + 4H2O Counter Electrode 2O2 + 8H + 8e
+ -

H2SO4 + 8H + 8e

4H2O

The most significant limitation of an electrochemical cell arises out of the consumptive nature of the device due to the gradual evaporation of its electrolytic medium. Much research has been undertaken to produce cells with improved resistance to evaporation. Some hydrogen sulphide detector manufacturers have recently demonstrated good performance with electrochemical cells in global desert environments such as the middle east. The key to their success has been improved detector construction and application knowledge.

Metal Oxide Semiconductor Metal Oxide Semiconductor (MOS) technology is probably the least understood commercially available mechanism to detect vapours. Their usage, since the technology was first discovered in the early 1950s has experienced greatest success in the domestic environment, initially through legislation passed in Japan. In the industrial sector their success has been limited to the detection of hydrogen sulphide and refrigerant gases.
6901 West 110th Street Minneapolis, Minnesota 55438 USA page 2 of 4 Tel: 952.941.5665 or 800.765.FIRE Fax: 952.829.8750 02-February 2000

Gas Detection Technical Note

Comparison of H2S Gas Detection Technologies
A MOS device usually comprises a gas sensitive resistive film, a platinum heater element and some insulation medium between the two. The gas sensitive film is traditionally made from a base material of Tin Oxide (SnO2) or Tungsten Oxide and combined with other metal oxides, catalysts or inhibitors in attempt to make the devices 2 more selective to a given target gas . The general schematic of such a device is given in Figure 3.

Figure 3: Semiconductor sensor schematic A MOS sensor produces a change in electrical conductivity due to the presence of gas/vapour. In clean air, oxygen is adsorbed at the surface striping electrons from the active material, forming a potential barrier at the intergrannular boundary, (shown in Figure 4), this causes the resistance to increase.

Figure 4: Grain boundary diagram

When a reducing gas is present e.g. hydrogen sulphide, the sensor surface adsorbs the vapour and is reduced, thus lowering the potential barrier and hence sensor resistance. This resistance change is non-linear and may be logarithmically correlated to the concentration of the gas/vapour present. The operating o temperature of MOS devices usually exceeds 100 C in attempt to speed up the rate of reaction, reduce ambient temperature effects and provide a degree of response selectivity. MOS sensors are able to detect a broad range of gases, including combustibles (e.g. methane). They offer greatest sensitivity at low concentrations (the exception being oxygen) and are typically initially faster responding than electrochemical cells. MOS sensors require regular calibration as they become insensitive over time, this is commonly known as going to sleep. This phenomena is not well understood and cannot be indicated by the instrument manufacturer, essentially making the device non-fail safe.
6901 West 110th Street Minneapolis, Minnesota 55438 USA page 3 of 4 Tel: 952.941.5665 or 800.765.FIRE Fax: 952.829.8750 02-February 2000

Gas Detection Technical Note

Comparison of H2S Gas Detection Technologies
When opting to use MOS devices consideration should be given to the environment where the unit will be used as they are affected by oxygen and humidity levels. Generally speaking, installation environments with significant seasonal changes in relative humidity will cause operator headaches with regards to repeatability during calibration routines.

Summary This paper has discussed the two most common technologies for the detection of hydrogen sulphide, namely electrochemical cell and metal oxide semiconductor. Electrochemical cell technology is mainly used to detect inorganic toxic gases as it offers exceptional stability and reliability. The cells are commonly used in both fixed and portable instruments but should not be used in applications where the target gas is normally present (high background levels) or in continuously anaerobic atmospheres. Electrochemical cells are direct measurement devices whereas MOS units are indirect. As a result, electrochemical cells do not require complex linearisation and zero offset compensation algorithms within the signal processing electronics MOS sensors are more suited to environments where the atmospheric conditions are fairly stable, thus negating the influences of relative humidity. The tendency for MOS devices to go to sleep is extremely undesirable and could lead to a potentially dangerous situation occurring. MOS devices are increasingly being used in applications where electrochemical cells would not normally be used, e.g. the detection of refrigerant gases. Gas detector manufacturers are increasingly replacing MOS sensors with the electrochemical cells. There are three principle reasons for this: a) b) Superior performance in terms of stability, accuracy and repeatability. Electrical circuit simplification, the measurement of sensor resistance, is by its very nature an indirect one, when combined with the non-linear gas response, electrical design engineers are increasingly changing to the direct output approach of an electrochemical cell. The technology has matured to the point where instruments are capable of demonstrating good performance in the Middle East.

c)

Written by:

Dr. Eliot Sizeland, Detector Electronics (UK) Limited

References 1 2 3. City Technology Limited, Product Data Handbook, Issue 4.0 January 1997. J. Watson, The Tin Oxide Gas Sensor and its Applications, Sensors and Actuators 5 (1984) pp2942. E. Sizeland, Ph. D Thesis, 1994, University of Southampton

6901 West 110th Street Minneapolis, Minnesota 55438 USA page 4 of 4 Tel: 952.941.5665 or 800.765.FIRE Fax: 952.829.8750 02-February 2000