Chapter 1

Introduction

Chapter 1

Introduction

T

he detection of hazardous gases has always been a complex subject and makes choosing an appropriate gas monitoring instrument a difficult task. To address this problem, this book aims to provide the following essential tools: • A simple guide to the various sensor technologies available • Information to help you intelligently select the proper instruments for specific applications • Information engineers can use to design a complete monitoring system • Technical data and practical procedures that technicians can use to check and maintain a gas monitoring system The main emphasis of the book is on gas detection technology that is used in the field of area air quality and safety. This field primarily involves the protection of personnel and property against toxic and combustible gases. The discussion includes the types of sensors used, the various instruments available, and the applications that incorporate these instruments.

1

Hazardous Gas Monitors

An Analytical Instrument. The example shown above automates gas chromatography with the help of its built-in robotic technology.
(Courtesy of CE Instruments)

Analytical Instruments and Monitoring Systems To date, no gas sensors exist that are 100% selective to a single gas. Achieving such selectivity requires the use of instruments that employ analytical techniques to identify gases. Examples of such instruments include Fourier transform infrared (FTIR) instruments that use the infrared spectral characteristics of gases, gas chromatographs that use analytical columns, and mass spectrometers that identify molecules through characteristic variable deflections from a magnetic field. These instruments provide fairly accurate and selective gas readings. Some typical applications for these kinds of instruments include airport bomb detection, drug abuse screening, and analyzing air pollutants. However, these analytical instruments require skilled and knowledgeable operators, and are generally very expensive and designed for laboratory tabletops or specific on-line applications for in-plant installations. In addition, many suffer from limitations such as high maintenance, slow response time, and large size, making them impractical monitors for area air quality and safety. Thus, they are typically used only as a last resort for applications in which a suitable sensor is not available. For work area air quality and safety applications, monitoring systems must meet a number of practical criteria. These monitoring systems must be: • rugged and corrosion-resistant • weather- and dust-proof • capable of being installed in hazardous areas • durable and long-term

A Gas Monitor. IST’s MP-204 is a wall-mounted unit housed in weatherproof enclosure with four sensor channels.

• operationally stable • easy to maintain • operated by a minimally skilled person
2

Chapter 1

Introduction

• suitable for multisensor systems that, for example, can be used for an entire chemical plant • low cost This book deals with gas monitors for work area air quality and safety applications. For practical purposes, we will not delve into the realm of the much more complex analytical instruments which, for the most part, do not meet these criteria. Gas Sensors A gas sensor is a transducer1 that detects gas molecules and which produces an electrical signal with a magnitude proportional to the concentration of the gas. Unlike other types of measurement, types that are relatively straightforward and deal with voltage, temperature, and humidity, the measurement of gases is much more complicated. Because there are literally hundreds of different gases, and there is a wide array of diverse applications in which these gases are present, each application must implement a unique set of requirements. For example, some applications may require the detection of one specific gas, while eliminating readings from other background gases. Conversely, other applications may require a quantitative value of the concentration of every gas present in the area. Types of Gas Sensors. There are many different technologies currently available for the detection of gases, each with certain advantages and disadvantages. The following sensing methods are the focus of our discussion and are the five types most suitable and widely used as gas monitors for area air quality and safety applications: • electrochemical • catalytic bead • solid state • infrared • photoionization

1

Any device that converts input energy of one form to output energy of another.
Gas Molecules

GAS TRANSDUCER

Electrical Signal

2

1

3

4

5 Some Examples of Gas Sensors
1. Catalytic Bead. 2. Infrared. 3. Solid State. 4. Electrochemical. 5. Photoionization.

3

Each sensor is sensitive to a group or a family of gases.P): The temperature at which a combustible liquid gives off enough vapor to form 4 . the sensor is non-specific and is subject to interference by other gases much like a smoke detector in a house cannot distinguish between the smoke caused by a furniture fire and the smoke caused by food burning in the stove or oven. a proper sensor is usually selected to match the specific application requirements and circumstances. is that they are not specialized to detect any one specific gas. an analytical column can be installed to identify chemicals qualitatively and quantitatively. a chemical filter can be installed to filter out interference chemicals while permitting the target gas to pass through to the sensor. opposite page) ppb: parts per billion by volume mg/m3: milligrams per cubic meter mg/cc: milligrams per cubic centimeter g/m3: grams per cubic meter g/cc: grams per cubic centimeter Ignition Source Fuel Oxygen The Combustion Triangle For Combustible Gases Flash Point (Fl. despite what is often claimed or implied. or for process control. Alternatively. In other words.Hazardous Gas Monitors All of these sensors are commonly used for detection of toxic and combustible gases in the work area for human and property protection. In limited cases. Terms. and Abbreviations Units of Measure for Gas Concentration ppm: parts per million by volume (see Table 1. with the user interpreting the readings based on an awareness of the sensor’s limitations. For gas monitoring applications. One common characteristic of these sensors. Definitions.

999 parts of background air. page 199. VT = total volume of air and gas Multiply the fraction derived from the formula above: a) by 102 % to obtain the percentage b) by 106 ppm to obtain the ppm c) by 109 ppb to obtain the ppb For example. if you mix 1 cc of gas with 99 cc of air. or ppb. Another unit. This volumetric expression of concentration is straightforward. It is expressed as Vg Vg = Va + Vg VT Vg = volume of gas.01 x 109 ppb = 10. Thus.01 x 102 % = 1% 0. Chemical conversion factors are included in the Gas Data section in Appendix II. For instance.Chapter 1 Introduction Table 1. is preferred. the ideal gas law must be used. commonly used in the medical and metallurgical industries. 5 . Equations for Deriving Units of Gas Concentration Gas concentration is commonly expressed as percent (%). one would normally not cumbersomely express the units as ten million parts per billion. Va = volume of air.01 1 cc + 99 cc 0. 1 psi of gas within 99 psi of air with total pressure of 100 psi has a concentration of 1% as in the volume expression. To convert mg/m3 to percent or ppm.000 ppm 0. 1%. Additionally. ppm. the volume ratio is equal to the pressure ratio according to Dalton’s law of partial pressures. Gas Sensor Calibration. the simpler expression.01 x 106 ppm = 10. It is expressed as Pg Pg Vg = = Pa + Pg PT VT Pg is the partial pressure of the gas within the total pressure PT and Pa is the partial pressure of air. these are unitless expressions since they do not carry a unit for volume or weight but simply express the ratio of gases in relation to background air. the calculation is as follows: 1 cc = 0.000 ppb = 107 ppb In cases like this. one ppm of CH4 simply means one part of methane amongst 999. Instead. is mg/m3 or milligrams per cubic meter.000. As an example. and the conversion formula is discussed on page 173 in Chapter 11. in situations wherein the chemical is either in liquid or solid state at room temperature. Mathematically.

The partial pressure curves of chemicals are available from chemical libraries or manufacturers of the chemicals. at room temperature) that will cause the propagation of flames when it comes in contact with an ignition source. + Pn H2O+ = 9% = 1.7 psi an ignitable and combustible mixture when air is present near the liquid’s surface. .29 psi P = PO2 + PN2 + PH2O+ P = 3. 1. That is. mixtures below the LEL or LFL are too lean to ignite. . is the sum of the independent pressures (partial pressures) that each gas exerts: P = P1 + P2 + . at room temperature) that will cause the propagation of flames when it comes in contact with a source of ignition.087 psi N2 = 70% = 10. Lower Explosive Limit (LEL) or Lower Flammable Limit (LFL): The minimum concentration of gas or vapor mixed with air (percent by volume. which do not react chemically.087 psi + 10.29 psi + 1. The combustible range is. Upper Explosive Limit (UEL) or Upper Flammable Limit (UFL): The maximum concentration of gas or vapor mixed with air (percent by volume. In common terminology. therefore. states that the pressure of a mixture of gases. In common terminology. between the LEL and the UEL (see Figure 1 below).323 psi P = 14.Hazardous Gas Monitors 2 The law of partial pressures. P. mixtures above the UEL or UFL are too rich to support combustion. 100% GAS CONCENTRATION (MIXTURE IN AIR) TOO RICH FOR COMBUSTION UEL COMBUSTIBLE MIXTURE LEL TOO LEAN FOR COMBUSTION 0% Fig.323 psi O2 = 21% = 3. A Window of Combustibility 6 . it is the temperature at which a combustible liquid chemical has sufficient partial pressure2 in the air to be ignited. first formulated by James Dalton in 1802.

S.Chapter 1 Introduction Specific Gravity (Sp. carbon dioxide.52.): The ratio of the weight per unit volume or mass of a substance at 68°F (20°C) to the mass of an equal volume of distilled water at 39. 1. toxicology.Gr. both components having the same temperature and pressure. it publishes recommended exposure limits (RELs) for hazardous substances or conditions in the work place.52. These recommendations are then published and transmitted to the Occupational Safety and Health Administration (OSHA) and the Mine Safety and Health Administration (MSHA) for use in promulgating legal standards. and propane. The American Conference of Governmental Industrial Hygienists (ACGIH) is a professional society. To formulate these recommendations. and analytical chemistry.2°F (4°C).55. Department of Health and Human Services. . 1.3 Vapor Density: The weight per volume of gas or vapor compared to dry air. Membership is limited to professionals in governmental agencies or educational institutions engaged in occupational safety and health programs in the United States and around 7 3 Water at 4°C has the LOWEST volume per gram. 0. not an official government agency. 0.07. Centers for Disease Control and Prevention. For Toxic Gases The National Institute for Occupational Safety and Health (NIOSH) is a branch of the U. air has a vapor density of 1. NIOSH collects and evaluates data from the fields of industrial hygiene. Acting under the authority of the Occupational Safety and Health Act of 1970 and the Federal Mine Safety and Health Act of 1977. OSHA published the permissible exposure limits (PELs) that are known as the General Industry Air Contaminants Standard. For example. Public Health Service. occupational medicine. hydrogen. Ice expands when its temperature goes below 0°C and will crack a rigid encasement of it even if it was made of cement. methane.

2 Simplified Three-Hour TWA. one hour. and the 0 1 2 3 time interval used by the HOURS instruments to calculate the Fig.7 ppm sented by the red line. yet in some instances there are variations among them. threshold limit values (TLV). hour. GAS CONCENTRATION (% MIXTURE IN AIR) 8 . This is a simplified version to illustrate the TWA concept. the TWA is: (50 ppm x 1 hr. Time-Weighted Average (TWA) is the average concentration of contaminants over a specified time period. ACGIH publishes the exposure standard.) (50 ppm x 3 hrs. It is beyond the scope of this book to include detailed discussions of each.) time period. These three different standards—NIOSH’s RELs. = 50 ppm under the concentration curve over time divided by Up to the end of the second hour. CO (50 ppm x 2 hrs.Hazardous Gas Monitors the world.) / 1 hr.7 ppm 3 50 ppm during the first The numbers within the parentheses represent areas under the curve. short-term exposure limit (STEL). To illustrate (50 ppm x 1 hr. then the CO concentration increases steadily to 100 ppm 100 100 ppm at the end of the third hour.25 ppm the concept of TWA (Figure 2 2). 50 56.25 ppm Many microprocessorTWA based instruments and data logging programs are capable of performing the 0 TWA calculation. let us assume that durUp to the end of the third hour. The TWA at any given moment is repre66.) + (50 ppm x 1 hr. The following definition of these terms are for informational purposes only. the TWA is: (25 ppm x 1 hr.) + 2 = 56. the TWA is: ing a three-hour period. Mathematically. All are based on time-weighted-average (TWA).) + concentration is constant at 2 = 66. ceiling (C) and immediately dangerous to life or health (IDLH) concepts. TWA is the integrated area During the first hour. OSHA’s PELs and ACGIH’s TLVs—are similar to each other. PELs are based on an eightTWA is much shorter than hour TWA.

or other health effects such as disorientation or incoordination that could prevent escape. The con0 5 10 15 cept of STEL is illustrated in FigMINUTES ure 3. Short-Term Exposure Limit (STEL) is defined as a fifteen-minute TWA exposure which should not be exceeded at any time during a work day even if the eight-hour TWA is within CEILING limits. for a normal eight-hour workday and a forty-hour work week. without adverse effects. The preceding information is a simplified version interpreted from the NIOSH Pocket Guide to Chemical Hazards. Fig. A graphical example of permitted TWA excursions Ceiling Limit: The concentration above STEL. There should be at least 60 minutes between successive exposures at the STEL. Exposures at the STEL should not be longer than fifSTEL teen minutes and should not be repeated more than four times TWA (red line) PEL per day. 3.Chapter 1 Introduction Recommended Exposure Limit (REL) is TWA concentration permissible for up to ten-hour workdays during a forty-hour work week. to which workers may be exposed continuously. Appendix II at the end of this book lists data 9 GAS CONCENTRATION (MIXTURE IN AIR) . at any time. day after day. irreversible health effects. Immediately Dangerous to Life or Health (IDLH) concentration is the maximum concentration above which only a highly reliable breathing apparatus providing maximum protection for workers is permitted. provided the 15-minute TWA does not exceed which should not be exceeded the STEL. The IDLH value is based on the ability of a worker to escape without loss of life. Permissible Exposure Limit (PEL) and Threshold Limit Value (TLV) are TWA permissible concentrations.

Hazardous Gas Monitors IDLH GAS CONCENTRATION (MIXTURE IN AIR) CEILING STEL PEL TWA extracted from the same pocket guide that includes REL. if the sum of the fractions of hazworking hours does not exceed PEL/TLV. For example. resulting in a final mixture that can be more toxic to humans than the individual toxicities of each gas. Observe the definition of STEL and never exceed the ceiling limit.. 4. This discussion is for conceptual purposes only. Figure 4 illustrates the overall summary of the toxic gas safety concept. Basic Rules for Compliance: TWA for eight is. When two or more hazardous substances 0 1 2 3 4 5 6 7 8 9 are present in the area. the calculation is as follows: 35 350 + = 0. then the PEL is exceeded.77 50 5000 The threshold limit is not exceeded. the additive HOURS effects should be considered. Combinations of Substances. Performance Specifications Accuracy: Webster’s dictionary defines accuracy as 10 . It does not take into account the effect of the combining of chemicals that can react with each other. if the ambient air contains 35 ppm of carbon monoxide (PEL 50 ppm) and 350 ppm of carbon dioxide (PEL 5000 ppm). That Fig. This case is illustrated in the following formula: C1 C C2 C + + 3 + . + n < 1 PEL1 PEL2 PEL3 PELn If it is greater than one.. C1. ardous substance concentrations divided by the respective PEL exceeds unity. then the threshold limit of the mixture must be considered excessive. PEL and IDLH concentrations.C2 and C3 represent the TWA of various hazardous substances.

In real life.Chapter 1 Introduction “the quality or state of being accurate or exact. standards for weight. each having its own unique chemical and physical properties. etc. Accuracy: Closeness of the agreement between the result of a measurement and a true value of the measurand. the weather thermometer. its accuracy is difficult to determine since 11 Measured Weight Standard Weight ACCURACY The International Vocabulary of Basic and General Terms in Metrology defines the terms for result of the measurement as follows: 1. After the mixture is made. there is no standard by which to compare accuracy. 3. e.” Accordingly.g. 4.99% air. Thus. . temperature. * measurand–a particular quantity subject to measurement. a measurement can be precise but not necessarily accurate. low tolerance. The definition of these measurement standards are well-defined. There are hundreds of different chemicals. With gas monitoring systems. the measuring tape which is used by the tailor is not very accurate. Accuracy is the most important definition of the quality of performance for most of the objects we deal with every day. your watch. length. The Challenge of Accuracy. Calipers used in a machine shop are more accurate than the tailor’s tape but would not be suitable for use by the tailor. Internationally. to name a few.* 2. Linear scale: Scale in which each spacing is related to the corresponding scale interval by a coefficient of proportionality that is constant throughout the scale. For example. minutely exact.” Accurate is defined as “free from mistake or error. and the measuring tape. this equates to 0. As an example. there is a total agreement about the “absoluteness” of those standards. The accuracy can only be determined when compared to a standard. what is 100 ppm of carbon monoxide (CO) in air? Mathematically. vapor pressure of a given sample of water at 20°C. Reproducibility: Closeness of the agreement between the results of measurements of the same measurand carried out under changed conditions of measurement. each instrument serves a different objective.. the bathroom scale. precise. exactness. The gas monitors serve more like a tailor’s tape than a machine shop’s caliper. are kept. etc. but it is practical for the task.” Precise is defined as “strictly defined. At the National Institute of Science and Technology (NIST. precision. adhering closely to a standard. for example. Repeatability: Closeness of the agreement between the results of successive measurements of the same measurand carried out under the same conditions of measurement. the most accurate instrument may not necessarily be the best. formerly National Bureau of Standards).01% of CO and 99.

gas monitoring sensors are put to work in “non-ideal” environments and. Ambient Air there is no standard 100 ppm of CO to compare with and there is no common agreement that defines a 100 ppm CO mixture. Zero Air: “Zero air” is available on the market in the form of a mixture of oxygen and nitrogen in a high pressure tank. and other trace gases. and there is no common understanding in general. accuracy is the most misunderstood and abused term in gas monitoring. however. it is best to establish a calibration method that can yield consistent and precise calibration data. The accuracy of this calibration method can be compared to an accepted standard when challenged. such as water vapor. In normal applications. most infrared (IR) detectors can be zeroed with dry air or N2 as long as the wavelength being detected has a minimum water vapor effect. Artificial Air or H2O O2 CO2 & N2 others B. there are many other components in the ambient air besides O2 and N2 . Because calibration standards are difficult to define in practice. with solid-state sensors or photoionization detectors (PIDs). Realistically. carbon dioxide. However. Some sensors can be zeroed with dry air or N2 but some cannot. As long as the calibrations are done with high precision. it is not practical to zero a sensor to a simple mixture of oxygen and nitrogen. For instance. There are few agreements amongst manufacturers of instruments. Therefore. Environmental Air Zero Air vs. the accuracy of your calibration can be established when an accepted standard is available. carbon monoxide. Repeatability: Repeatability is the ability of sensors to repeat the measurements of gas concentrations when the sensors are subjected to precisely calibrated gas samples. very different 12 . consequently.Hazardous Gas Monitors O2 N2 A.

For example. but as the gas concentration increases. the surface temperature of the sensor can be set differently in order to make it more sensitive to one gas and less sensitive to other gases. a charcoal filter is used to filter out most hydrocarbons while letting only CO. the initial output of the sensor is linear or close to it. The most common practice is to use an analytical column. Most sensors are sensitive to a family of gases. Thus. Among the more specific sensors is an electrochemical sensor for the detection of oxygen. As the gas concentration increases. . and there are no sensors specific to only one gas. this is the easiest way to verify whether a sensor is giving a real alarm Sensor Output or a false alarm. With most sensors. resulting in poor resolution. Most sensors provide better accuracy at lower concentrations than at very high concentrations. Specificity or Selectivity: This is the ability of an instrument to detect a target gas without being affected by the presence of other interfering gases. 5.Chapter 1 Introduction readings may result from dry air compared with wet air. instruments on the market today commonly have output signals that are digitally linearized. the output signal is gradually reduced. sensors may be satisfactorily zeroed by exposing the sensor to a bag of air collected from a location where the air is “normal. then the output will be linLinear 5 ear. H2. In many applications. linearity refers 10 to the output signal in relation to the gas concentration: If 1 volt equals 10 ppm and a full scale 5 volts represent Near 50 ppm. Typical Sensor Output Curve. In solid-state sensors. Figure 5 shows a typical sen0 sor response curve. the output signal becomes smaller in relation to the increase in gas concentration. in which the gas sample stream is introduced into the column and the chemical 13 Nonlinear Saturation (Poor Resolution) Gas Concentration Fig. Different techniques are employed in order to achieve some degree of selectivity to suit practical applications. in volts Linearity: Quantitatively. and CH4 pass through.” In fact.

even though it is stated that a certain gas will not interfere. Therefore. you should inquire with the manufacturer if the sensor is selective to a spe14 . it is not possible for manufacturers to present data on cross sensitivity ratios for all gases. when the concentration is increased to 1. on a 100 ppm carbon monoxide sensor. This method works well for laboratory use but has proven to be impractical for gas monitoring because it requires a high degree of user knowledge and a high degree of maintenance. For instance.Hazardous Gas Monitors components are separated and come out at the end of the column at different times. since the sample must be drawn through the column. sensors are not selective to a single gas and will read other gases as well. if the concentra9 ppm H2 shows as 3 ppm CO tion of this gas is high enough. where they are detected by a sensor. Sample times of 15 to 30 minutes are not unusual. if interference data is not provided for a gas that is of interest to you. In many cases. Additionally. This means that 3 ppm of 33 ppm CO Sensor CO Signal H2 will read the same as 1 ppm of CO. a common practice for manufacturers of gas monitoring equipment is to pro9 ppm 30 ppm vide data indicating the ratios that different gases H2 CO will read on the sensor. Thus. For ambient air monitoring. while a CO sensor with a charcoal filter has little interference from certain solvents at 100 ppm. the time necessary to take readings can be relatively excessive. it is much more practical to use a sensor directly installed at the location being monitored and compensated for the different gases which may be present. they may interfere drastically. Because there are so many gases. Interference Ratio: As mentioned earlier.000 ppm. For example. it may in fact actually interfere. hydrogen may read at a 3-to-1 ratio.

the possible water condensation and resultant corrosive mixtures can compromise the life expectancy of a sensor. Response/Recovery Time: This is typically defined as the time it takes for a sensor to read a certain percentage of full-scale reading after being exposed to a full-scale concentration of a given gas.Chapter 1 Introduction 100% Scale 50% 0% T80 T100 Time Fig. For example. water vapor is present at a level of 3%. at 80% relative humidity and a temperature of 25°C. However. but beware of the humidity specification. Quantitatively. combined with the changing of temperature between day and night. 15 . the manufacturer could provide the data needed. For instance. the same 80% relative humidity at a temperature of 48°C produces a water vapor level of 10%. In the presence of chemicals. Temperature and Humidity: Specifications for these parameters are easy to understand. A Typical Sensor Response cific gas being targeted. in which case. Relative humidity is an indication of the amount of water vapor in air as a percentage of the total amount possible at a given temperature. T80 = 30 seconds means that the sensor takes 30 seconds to reach 80% of the fullscale reading after being exposed to a full-scale gas concentration.6. the amount of actual water vapor in air is a function of temperature.

the following information may be helpful. will indicate 50 ppm. the alarm will not turn off until the gas is below 90 ppm. typically 30 days or more. Most infrared and photoionization instruments do not exhibit hysteresis. This variation of 5 ppm is 5% full-scale hysteresis. when calibrated from 0 to 50 ppm and exposed to a 50 ppm calibration gas. Industrial facilities in which potentially explosive gas atmospheres exist or may exist must utilize proper explosion proof protection methods when using these types of instruments. a 100 ppm instrument. solid state. however. if the alarm comes on at 100 ppm. The reader is advised to consult with the manufacturer for specific needs.Hazardous Gas Monitors Hysteresis: The difference in response of the sensor when calibrating from a zero level to mid-scale compared to the response when calibrating from full scale to mid-scale. Hazardous Locations Gas monitoring instruments are often installed in industrial process and production areas. is known as hysteresis. including electrochemical. These areas are often classified as hazardous locations. For example. North America and other parts of the world that 16 . and catalytic sensors do exhibit hyteresis. In alarm setting. the difference between the on point and off point alarm is also referred to as hysteresis. This quantity is normally expressed as a percentage of full scale. However. For instance. It is beyond the scope of this book to provide full details. Zero and Span Drift: While there is no specific definition for these two terms. otherwise. when the sensor is calibrated to 100 ppm gas but is exposed to 50 ppm the sensor may indicate 55 ppm. This hysteresis is needed. an alarm can be chattering at the set point of 100 ppm. but many other sensors. common understanding holds that this drift is the percentage change of the zero or span calibration over a specified period of time.

There are four different groups in Class I. or the Ca® nadian Standards Association (CSA ). Divisions define the condition under which the hazardous material North American Certification Agencies may be present. such as acci17 . ignition temperature. Division 2: Where ignitable concentrations of gases. combustible dusts. butadiene. and fibers can exist all the time or some of the time under normal operating conditions. Hazardous conditions only exist in the event of abnormal conditions. formaldehyde.Chapter 1 Introduction have been influenced by North American practices have traditionally used the National Electric Code(NEC®) articles 500-503. propylene oxide. They employ a class and division system: Classes identify the type of hazard present as gases or vapors. dusts. and pressure generated during explosion of various gases and vapors. and fibers do not exist under normal operating conditions. and flammable fibers. and propyl nitrate Groups C and D: All other combustible gases belong to Groups C and D Division 1: Where ignitable concentrations of gases. hydrogen. dusts. The NEC 500 hazard classifications are as follows: Class I: Flammable gases or vapors. vapors. The devices designed and manufactured for these hazardous locaUnderwriters Laboratories Factory Mutual tions should be tested and approved for use by a nationally recognized laboratory such as Under writer’s Laboratories Canadian Standards Association (UL®). Factory Mutual (FM). vapors. Class II: Combustible dusts Class III: Easily ignitable fibers and flyings Groups are based on flame propagation characteristics. These groups are as follows: Group A: Acetylene Group B: Acrolein. ethylene oxide.

and 2 based on the probability of occurrence and length of time a potential explosive mixture may be present. The IEC separates the potentially explosive atmosphere into Zones 0. and if it does. C and D hazardous locations for use in North American markets. 21. as well as a majority of other nations of the world. it will exist for a short period only. A brief comparison of IEC (world). Zones 20. National Fire Protection Agency (NFPA) in America adopted article NEC 505 which is comparable to IEC standards.Hazardous Gas Monitors CENELEC Marking Example: Approved mark for apparatus certified by an EC test authority Symbol for apparatus built in accordance with a European standard Flameproof enclosure (type of protection) Explosion group Temperature class Ex EEx d IIb T3 dental rupture or breakdown of a container. and 2 that refer to ignitable dust clouds. Zone 1: An area in which an explosive gas atmosphere is likely to occur in normal operation. In accordance with their explosive properties. European countries. Zones. 1. Condition: Hazardous conditions exist continuously 18 . storage tank. There are no direct comparisons between the current NEC and IEC standards. the combustible gases and vapors are divided into temperature classes and explosion protection subgroups. etc. Division 1. CENELEC (Europe) and NEC (USA) are as follows: 1. Group B. Apparatuses designed for use in these areas are usually tested and approved for use by the European Committee for Electrotechnical Standardization (CENELEC) test authorities using Euronorm (EN) standards. Gas monitoring instruments are typically designed and certified for use in Class I. and 22 are a subset of Codes 0. The division of these three zones are: Zone 0: An area in which an explosive gas atmosphere is continuously present for long periods. Definition Comparisons. Zone 2: An area in which an explosive gas atmosphere is not likely to occur in normal operation. 1. have been influenced by the International Electrotechnical Commission’s (IEC) three-tiered zone approach.

Chapter 1 Introduction or for long periods of time.Class 1. The enclosure joints and structure covers are designed and manufactured for such purposes. AExd. Division 1 & 2. NEC 505: Class 1. Division 1 IEC: Zone 0. without causing ignition of an external explosive atmosphere. CENELEC-EExd. Fig. An Explosion-Proof Enclosure . Zone 0 NEC 500: Class 1. Division 1 IEC: Zone 1 CENELEC: Zone 1 3. IEC-Exd. Condition: Hazardous condition is not likely to occur in normal operation and if it does. The more common types are the following: A. such as the one shown in Figure 6. will withstand an internal explosion. 19 4 The lower case letter in a CENELECapproved marking designates the type of protection offered by an enclosure. Flameproof Enclosure (d)4 : The enclosure. Zone 2 NEC 500: Class 1. Division 2. Zone 1 & 2. This type of protection is most commonly used for gas monitoring applications and can meet the requirements of: NEC 500 . NEC 505: Class 1. NEC 505: Class 1. NEC 505-Class 1. CENELEC: Zone 0 2. IEC: Zone 2 CENELEC: Zone 2 Types of Protection There are several acceptable types of protection for electrical equipment in hazardous locations. Condition: Hazardous condition is likely to occur in normal operation. 6. only infrequently and for a short period. Zone 1 NEC 500: Class 1.

Hazardous Gas Monitors Types of Flamepaths in Flameproof Enclosures Joint Threaded Spigot Materials used: Aluminum. These are limited to low power device applications only.Exi(a). in any worst case scenario. Iron (Courtesy of Cullen Associates) HAZARDOUS AREA SAFE AREA Single Channel Resistor Zener Diodes Fuse Sensor Module Intrinsically Safe Ground (Courtesy of Cullen Associates) B. CENELEC . Division 1 & 2.Class 1. 20 . Intrinsic Safety (i): The electrical energy in an intrinsically safe circuit which enters into the enclosure is not sufficient to generate a spark and ignite a combustible mixture in the hazardous area. power Power supply must resistors. safety barriers or other devices limiting the electrical energy are placed on the wires to Process limit the electrical energy alController lowed to flow through the cir(+) 24 v cuit before the wire enters into the hazardous location.EExi(a). Various approved and certified safety barriers are available as standard electrical components. IEC . This method of protection can meet the requirements of: M NEC 500 . Safety barriers are a combiR nation of zener diodes. 1 & 2. Zones 0. and fuses which are not be grounded designed to limit the amount of electrical energy allowed to flow through the wires. To meet this requirement.Class 1. AExi(a). NEC-505 .

NEC 505 .No Standard. Type Y pressurizing: Reduces the classification within the protected enclosure from Division 1 to Division 2 or Zone 1 to Zone 2.Exp. AExe. Zone 2 to unclassified. D.Class 1.Exe. IEC . IEC . Pressure Regulator This type of protection can meet the requirements of: NEC 500 . CENELEC . Zone 1 & 2.Chapter 1 Introduction C. CENELEC . 21 . Purged and Pressurized (p): This is the process of supplying sealed electrical enclosures with a protective gas to prevent the entrance of flam.EExe. Division 1 or Class 1. Division 2 or Class 1. Type Z pressurizing: Reduces the classification within the protected enclosure from Class 1. Y & Z. NEC 505 . in which additional measures are applied so as to give increased security against the possibility of excessive temperature and of the occurrence of arcs and sparks. Optional Pressure Relief Device Pressure Indicator Protective Enclosure Optimal Alarm or Power Cut-Off Switch Type X pressurizing: Reduces the classification within the protected enclosure from Class 1.Type X.Type X.Protective mable gases while Gas Supply maintaining a positive enclosure pressure. This method of protection can meet the requirements of: NEC 500 .EExp. Y & Z. Zone 1 to unclassified. Increased Safety (e): This is a type of explosion protection applied to electrical apparatus that does not produce arcs or sparks in normal service.

C. as well as formation of ice on the enclosure. Class II. it is for indoors or outdoors. and G. NEMA Type 4X: Same as NEMA Type 4. Class 1. provides protection against incidental contact with the enclosed equipment. NEMA Type 9: For indoor use in dust applications. provides protection against a limited amount of falling water and dirt. NEMA Type 4: Same as NEMA Type 3. B. but it also provides corrosion resistance for indoor use. rain and sleet. except. Provides protection against windblown dust.Hazardous Gas Monitors E. Groups A. the National Electrical Manufacturer’s Association (NEMA). and D. F. NEMA Type 3: For outdoor use. NEMA Type 2: In addition to NEMA Type 1. Enclosure Classifications For Nonhazardous Areas In North America. This rating system identifies the ability of the enclosure to resist various possible conditions. but provides protection against water during temporary submersion at a limited depth. Provides rust resistance. NEMA Type 3R: Same as NEMA Type 3. 22 . but does not provide dust protection. Groups E. powder filling(q) and moulding(m). NEMA Type 7: For indoor use in hazardous locations. classified the enclosures in different ratings which are intended to provide information for users to make proper product choices. Other Protection Methods: Oil immersion(o). The classifications are as follows: NEMA Type 1: For general-purpose indoor use. as a way of standardizing enclosure performance. NEMA Type 6: Same as NEMA Type 4X. provides protection against direct water hose down.

the IEC enclosure classification designations cannot 23 . provides protection against dust.5 mm Granular objects of more than 1 mm diameter Dust protected. spraying water. NEMA Type 13: For indoor use. Internationally. The definitions for protections are different from that of NEMA. not completely tight Dust tight Second Digit No protection Vertically falling water Falling water at up to 15 degrees from vertical Falling water up to 60 degrees from vertical Water splashes from any direction Water from a nozzle from any direction Powerful water jet Short-term immersion Continuous immersion The IP classification is set by the International Electrotechnical Commission. Protection 0 1 2 3 4 5 6 7 8 First Digit No protection Large objects of more than 50 mm diameter Medium-sized objects of more than 12 mm diameter Small objects of more than 2. and dripping noncorrosive liquids. and noncorrosive coolant. The first digit (0-6) defines the protection against contact and entry of foreign objects while the second digit (0-8) defines the protection against water. provides protection against dust.Chapter 1 Introduction NEMA Type 12: For indoor use. falling dirt. oil. Therefore. the protections for electrical apparatuses are designated with ingress protection (IP) followed by a two-digit number which defines the degree of protection.

It is important to understand the terms used. the examples of chemical toxicity presented in this book do not consider the complexity of actual toxicology and interreactions between contaminant chemicals. a specialist on the subject needs to be consulted. the concept of the units used in the measurements and the definition of terminologies is somewhat unique. IP 67 is equivalent to NEMA 6. IP 66 is approximately equivalent to NEMA 4 or 4X . The distinction between the two is based largely upon their usage in the actual application. 24 . In critical applications. For this type of safety application. and IP 55 is equivalent to NEMA 12. Summary There is no clear definition delineating a gas monitor from an analytical analyzer. However. As examples. A gas monitor is most frequently used to monitor gases in toxic and combustible ranges for area air quality and safety applications.Hazardous Gas Monitors be exactly equated with NEMA enclosures.

geometry. By the mid-1980s. Electrochemical Sensors . and the construction of an electrochemical sensor usually depends on its intended use. In fact. the appearance of the electrochemical sensors used to detect various gases may be similar. The physical size. Figure 1 shows a small collection of such electrochemical sensors.Chapter 2 Electrochemical Sensors Chapter 2 Electrochemical Sensors T he oldest electrochemical sensors date back to the 1950s and were used for oxygen monitoring. selection of various components. but their functions are markedly different. the final design results in a compromise between various performance parameters of the electrochemical sensor. More recently. with the sensors exhibiting good sensitivity and selectivity. 27 Fig. a variety of electrochemical sensors are being used extensively in many stationary and portable applications for personal safety. as the Occupational Safety and Health Administration (OSHA) began requiring the monitoring of toxic and combustible gases in confined space applications. Quite often. new and better electrochemical sensors have been developed. The most common misconception about electrochemical sensors is that they are all the same. Currently. 1. Consequently. miniaturized electrochemical sensors became available for detection of many different toxic gases in PEL ranges.

However. one can achieve the selectivity towards the target gas. the electrolyte composition and the sensing electrode material is selected based on the chemical reactivity of the target gas. A typical electrochemical sensor conReference Electrode sists of a sensing electrode (or working elecCounter Electrode trode).Hazardous Gas Monitors Gas Molecules Anode + Micro Ammeter Cathode – Electrolyte Fig. but the sensitivity may be reduced. this design also allows more of the electrolyte’s water molecules to escape out to the environment. selectivity. By careful selection of the electrolyte and/or the sensing electrode. Figure 3. For example. 2 Basic Sensor one can expect varying performance from each of these sensors. an electrochemical sensor with high sensitivity would have a relatively short operating life due to evaporation of moisture through the porous membrane. and porosity of hydrophobic barriers. Typical Electrochemical Sensor Setup Gas that comes in contact with the sensor 28 . All components of the sensors play a crucial role in determining the overall characteristics of the sensors. 3 Principle of Operation Electrochemical sensors operate by reacting with the gas of interest and producing an elecHydrophobic Membrane trical signal proportional to the gas concenSensing Electrode tration. but are constructed with different materials including such critical elements as sensing electrodes. and operating life. and a counter electrode separated by a Electrolyte thin layer of electrolyte. Similarly. In summary. in terms of sensitivity. a low concentration gas sensor with very high sensitivity uses a coarse-porosity hydrophobic membrane and less restricted capillary to allow more gas molecules to pass through to produce enough signal for better sensitivity. In other words. response time. Additionally. different electrochemical sensors may appear very similar. electrolyte composition. Capillary Diffusion Barrier Fig. some electrochemical sensors use external electrical energy to make them reactive to the target gas.

To improve the performance of the sensor.Chapter 2 Electrochemical Sensors first passes through a small capillary-type opening and then diffuses through a hydrophobic barrier. The gas molecules react at the sensing electrode and the current flow between the sensing and the counter electrode is measured and is typically related directly to 29 Water and Gas Hydrophobic Membrane Gas Electrolyte Fig. It causes deterioration of the performance of the sensor over extended periods of time. . Because a current is generated in the process. In reality. This approach is adopted to allow the proper amount of gas to react at the sensing electrode to produce a sufficient electrical signal while preventing the electrolyte from leaking out of the sensor. The reference electrode maintains the value of this fixed voltage at the sensing electrode. and eventually reaches the electrode surface. No current flows to or from the reference electrode. the sensing electrode potential does not remain constant due to the continuous electrochemical reaction taking place on the surface of the electrode. Importance of a Reference Electrode. Figure 4. a current proportional to the gas concentration flows between the anode and the cathode. A fixed stable constant potential is applied to the sensing electrode. 4 Hydrophobic Membrane: prevents liquid electrolyte from leaking out. These reactions are catalyzed by the electrode materials specifically developed for the gas of interest. it is important to have a stable and constant potential at the sensing electrode. This reference electrode is placed within the electrolyte in close proximity to the sensing electrode. The current can be measured to determine the gas concentration. With a resistor connected across the electrodes. the electrochemical sensor is often described as an amperometric gas sensor or a micro fuel cell. The gas that diffuses through the barrier reacts at the surface of the sensing electrode involving either an oxidation or reduction mechanism. For a sensor requiring an external driving voltage. a reference electrode is introduced.

an electrochemical sensor specific to oxygen has an anode. the sensing electrode is covered with a high-porosity Teflon and the amount of gas molecules reaching the electrode surface is controlled by a capil30 . either Pb or Cd. These types of sensors do not require a reference electrode. in some instances. Such barriers are typically made of thin. the electrons are released which then travel via an external circuit to the cathode where oxygen molecules consume the electrons as follows: In acidic electrolyte Oxidation at the anode: 2Pb + 2H2O → 2PbO + 4H+ + 4e- Reduction at the cathode: O2 + 4H+ + 4e. Major Components An electrochemical sensor consists of the following major components: A. to control the amount of gas molecules reaching the electrode surface. The value of the voltage applied to the sensing electrode makes the sensor specific to the target gas. Gas Permeable Membrane (also called hydrophobic membrane): This is used to cover the sensor’s sensing (catalyst) electrode and.→ 2PbO + 2H2O + 4eReduction at the cathode: O2 + 2H2O + 4e.→ 2H2O In basic electrolyte Oxidation at the anode: 2Pb + 4OH. During the oxidation of the anode. Alternatively. that supplies electrons for the reduction of oxygen at the cathode.→ 4OHThe overall reaction in both cases is: 2Pb + O2 → 2PbO.Hazardous Gas Monitors the gas concentration. Such sensors are called membrane clad sensors. low-porosity Teflon membranes. The micro fuel cell-type electrochemical sensors do not require an external driving voltage. For example.

Filter: Sometimes a scrubber filter is installed in front of the sensor to filter out unCapillary wanted gases. all three electrodes can be made of different materials to complete the cell reaction. the sensor’s signal will deteriorate. and catalyzed for an effective reaction with gas molecules. Typically. There is a limited selecDiffusion tion of filters. The pore size should also prevent liquid electrolyte from leaking out or drying out the sensor too quickly.Chapter 2 Electrochemical Sensors lary. Besides offering a mechanical protection to the sensor. D. The pore size should be such as to allow enough gas molecules to reach the sensing electrode. an elec31 . If the electrolyte evaporates too quickly. 5 Filtering with Activated Charcoal selecting the filter medium. each with different deBarrier Charcoal Filter grees of effectiveness. the membrane performs the additional function of filtering out unwanted particulates. the electrode is made from a noble metal. such as platinum or gold. The acReference Electrode tivated charcoal filters out most chemiCounter Electrode cals with the exception of carbon monElectrolyte oxide and hydrogen gases. Such sensors are referred to as capillary-type sensors. Electrode: The selection of the electrode material is very important. B. By properly Fig. C. Electrolyte: The electrolyte must facilitate the cell reaction and carry the ionic charge across the electrodes efficiently. Selecting the correct pore size of the membrane and capillary is necessary to transfer the proper amount of gas molecules. It is a catalyzed material which performs the half cell reaction over a long period of time. Depending on the design of the sensor. It must also form a stable reference potential with the reference electrode and be compatible with materials used within the sensor. The most comSensing Electrode monly used filter medium is activated charcoal. as shown in Figure 5.

Cl2 Chlorine Dioxide. Such sensors do not require the presence of oxygen to function properly. NO Nitrogen Dioxide. Minor variations in the details of the sensor design can have a profound influence on the sensor’s accuracy. hence the sensors will not operate properly.→ NO + H2O Cl2 + 2H+ + 2e. NO2 Oxygen Ozone. and ozone—at the cathode produce water as a byproduct.Hazardous Gas Monitors Typical Gases and the Range of Measurement of Electrochemical Sensors GAS NAME Ammonia. O3 Phosphine. B2H6 Fluorine. CO Chlorine. chlorine. SO2 PPM RANGE 10 1 30 300 5 5 1 10 2 2000 30 30 10 30 100 50 ppm levels to 100% by vol. Br2 Carbon Monoxide. HCl Hydrogen Cyanide. GeH4 Hydrogen. At the anode. water is simultaneously oxidized. SiH4 Sulfur Dioxide.→ 2H2O An inadequate supply of oxygen to complete the reaction will shorten the life of the sensors. sensitivity. NH3 Arsenic Hydride. HCN Hydrogen Fluoride. and life expectancy. H2 Hydrogen Chloride. Importance of Oxygen. AsH3 Bromine. ClO2 Diborane.→ 2HCl O3 + 2H+ + 2e. HF Hydrogen Sulfide. the reactions at the counter electrode (cathode) need oxygen molecules to complete the process: O2 + 4H+ + 4e. PH3 Silane. Sensors involving a reduction reaction of the target gas—such as the reduction of nitrogen dioxide. The reactions at the sensing electrode(anode) for some gases are as follows: CO + H2O → CO2 + 2H+ + 2eH2S + 4H2O → H2SO4 + 8H+ + 8eNO + 2H2O → HNO3 + 3H+ + 3eH2 → 2H+ + 2e2HCN + Au → HAu(CN)2 + H+ + eSimultaneously. H2S Nitric Oxide. selectivity. Choosing the suitable materials for the above components.→ O2 + H2O 32 . response time. as shown by the following: NO2 + 2H+ + 2e. 3 1 50 100 trochemical sensor can be made more selective to its target gases. F2 Germane. and arranging the geometry of all these components to determine the optimum operating performance presents a challenge to scientists.

33 . There is a vent hole on the side or back of the sensor for this purpose. the sensors are shipped from the factory with a nine-volt battery powered electronic circuit. It is wise to double-check with the manufacturer in applications that use nonoxygen background gas. Two-electrode sensors do not require any bias voltage. even if the instrument is turned off. For example. It takes anywhere from thirty minutes to twenty-four hours for the sensor to stabilize. and in such cases. oxygen sensors do not require a bias voltage. Most of the toxic gas sensors require a small amount of oxygen to function properly. there is normally a jumper which connects the working and reference electrodes. the sensor cannot be removed from power for an appreciable amount of time. and it will continue to stabilize over a three-week period. However. With a three-electrode sensor. the main characteristics of the sensors are essentially very similar. Following are some of the common characteristics of electrochemical sensors: 1. 2. When installed in a portable or stationary instrument. Some sensors require a bias voltage between the electrodes. If it is removed during storage.Chapter 2 Electrochemical Sensors Characteristics There are many different ways that electrochemical sensors are constructed. depending both on the gas to be detected as well as the manufacturer. it will take a long time for the sensor to stabilize and be ready to be used. It is wise to double-check the instrument before use if batteries or power were removed at some point. The portable instrument’s circuitry provides a small current needed to maintain the sensor in the ready-to-use condition.

3:1 2:1 3. However. it will read lower. just as other gas molecules can. Electrochemical sensors are also quite sensitive to temperature and. the sensors are typically internally temperature-compensated. it is better to keep the sample temperature as stable as possible.5% to 1.6:1 2:1 10:1 20:1 10:1 10:1 2:1 The higher the interference ratio.0% per degree centigrade.3:1 1. Sensors that are designed to monitor high gas concentrations have less porous barriers to limit the amount of gas molecules that pass through. which have more porous barriers and allow a more free exchange of water molecules. it is important to keep the entire sensor within the same pressure since differential pressure within the sensor can cause sensor damage. Selectivity Electrochemical sensors are generally fairly selective to the target gas they are designed for. Electrolyte within the sensor cell is an aqueous solution separated by a hydrophobic barrier which will not allow the aqueous solution to leak out. when the temperature is above 25°C. therefore. However. In high humidity conditions. In general. the target gas. water vapor can pass through. depending on the manufacturer and type of sensor. The temperature effect is typically 0. In low humidity conditions. and therefore are not affected by the humidity as much as sensors that are used to monitor low gas concentrations. the sensor will read higher. However. the less effect an interference gas has on the sensor. The degree of selectivity depends on the type of sensor. prolonged exposure can cause excessive water to build up and create leakage.Hazardous Gas Monitors 3. and the concentration of gas the sensor is 34 List of Typical Gas Interference Ratios for CO Sensors Gas H2S SO2 NO NO2 H2 Without Filter With Filter 0. when it is below 25°C. . the sensor can dry out. Pressure and Temperature Electrochemical sensors are minimally affected by pressure changes.

In reality. temperature. Typical Toxic Gas Electrochemical Sensor Specification Sensor Type: 2 or 3 electrodes. which has good selectivity. and humidity to which it is exposed. mostly 3 electrodes Range: 2-10 times permissible exposure limit Life Expectancy: 12 to 24 months normal. Other electrochemical sensors are subject to interference from other gases. interference concentrations can be quite high. Long Term Drift: drift down 2% per month 35 . They are the most popular sensors in confined space applications. the life expectancy of the sensor is highly dependent on the environmental contaminants. including the gas to be detected and the environmental conditions in which the sensor is used. Summary Electrochemical sensors require very little power to operate.Chapter 2 Electrochemical Sensors designed to detect. a one. such as temperature. pressure and humidity. However. causing false readings and/or alarms. is very reliable. depends on manufacturer and sensor Temperature Range: –40oC to +45oC Relative Humidity: 15-95% noncondensing Response Time T80 : < 50 sec. In fact. The higher the ratio. the sensors are widely used in portable instruments that contain multiple sensors. A sensor’s life expectancy is predicted by its manufacturer under conditions that are considered normal. Generally. their power consumption is the lowest among all sensor types available for gas monitoring. A typical list of interference ratios for CO sensors is shown on page 34 as an example. as well as other environmental conditions. For this reason.to three-year life expectancy is specified. Life Expectancy The life expectancy of an electrochemical sensor depends on several factors. The interference data are taken using relatively low gas concentrations. The best electrochemical sensor is for the detection of O2. and has a long life expectancy. In actual applications. the life expectancy will be highly dependent on the total amount of gas exposed to the sensor during its life. the less the effect of interference gas on the sensor.

volcanic rock. This phenomenon is known as a catalytic combustion. Most metal oxides and their compounds have these catalytic properties. where they replaced canaries that had been used for a long period of time. For instance. which is comprised of various metal oxides. This is not only decorative. A catalytic bead sensor is shown in Figure 1. as used in the original design. However. In its simplest form. Initially. 1 A Catalytic Bead Sensor Principle of Operation Combustible gas mixtures will not burn until they reach an ignition temperature. but the performance and reliability of these sensors varied widely among these various manufacturers. Catalytic bead sensors were produced all over the world by a large number of different manufacturers. but it also helps 37 . the gas will start to burn or ignite at lower temperatures. Fig. They have been in use for more than 50 years. The sensor itself is quite simple in design and is easy to manufacture. in the presence of certain chemical media. it was comprised of a single platinum wire. is often placed in gas burning fireplaces. these sensors were used for monitoring gas in coal mines.Chapter 3 Catalytic Combustible Gas Sensors Chapter 3 Catalytic Combustible Gas Sensors C atalytic bead sensors are used primarily to detect combustible gases.

its Ct is linear between 500°C to 1000°C. 2 A catalytic bead sensor Wheatstone bridge–a circuit for measuring an unknown resistance by comparing it with known resistances. This explains why the automobile exhaust system is treated with platinum compounds and is called a catalytic converter. and therefore is called the catalytic gas sensor. Platinum. All electrically conductive materials change their conductivity as temperature changes. Wheatstone bridges are commonly used in many electrical measurement circuits. It is corrosion resistant and can be operated at elevated temperatures for a long period of time without changing its physical properties. Platinum has a large Ct in comparison to other metals. palladium. the combustion process and results in cleaner and more efficient burning in the fireplace. This is called the coefficient of temperature resistance (Ct). platinum possesses excellent mechanical properties.C. Furthermore. platinum has excellent chemical properties. in honor of English physicist and inventor Sir Charles Wheatstone (1802-75). Because the signal from the sensor is linear. POWER Fig. A gas molecule oxidizes on the catalyzed surface of the sensor at a much lower temperature than its normal ignition temperature. which is the temperature range at which the sensor needs to operate. and thoria compounds are also excellent catalysts for combustion.Hazardous Gas Monitors OUTPUT ea RB R1 RB D. In addition. four circuit branches are arranged 38 Ac tiv eB d Re fe re nc eB ea d . As shown in Figure 2. It is expressed as the percentage of change per degree change in temperature. Also. This improves the accuracy and simplifies the electronic circuitry. this means that the concentration of gas readings are in direct proportion to the electrical signal. This kind of gas sensor is made on the basis of the catalytic principle. It is capable of producing a constant reliable signal over an extended period of time. The electrical circuit used to measure the output of catalytic sensors is called a Wheatstone bridge. It is physically strong and can be transformed into a fine wire which can be processed into small sensor beads.

The original catalytic sensor was a coil-shaped platinum wire. It is important that the reference sensor or bead maintains a constant resistance during the exposure to the combustible gas. Evolution of the sensor. and. and between the other pair of opposite corners. Resistor value RB and trim pot R1 are selected with relatively large resistance values to ensure proper function of the circuit. but should be nonreactive with the 39 Fig. In operation. This causes a reduction in the cross-section of the platinum wire. the measured signal will be inaccurate. Unfortunately. At this temperature. R1 is the trim resistor that keeps the bridge balanced. which in turn changes the resistance of the sensor. The source of the electrical current is connected. As the bridge is unbalanced. despite the excellent physical and chemical properties of platinum. When the gas burns on the active sensor surface. 3 Hot Wire Sensor . the resistance increases. the heat of combustion causes the temperature to rise. The reference wire ideally should be the same as the active wire. the output measurement circuit is connected. For the proper detection of hydrocarbon gases. with the same geometry and operating temperature. the platinum starts to evaporate. otherwise. was used to obtain a compact geometry for efficient heating and to produce a strong enough signal to function as a gas sensor. illustrated in Figure 3. it is a poor catalyst for combustion of hydrocarbon gases. The coiled shape. however. as a result. A balanced bridge has no output signal. the sensor requires a heated surface temperature between 900°C and 1000°C so that the sensor can properly react with gases at a sufficiently high and stable rate. The evaporation rate increases as the gas molecules start to react with the sensor and as the sensor temperature increases. This affects the sensor’s operating temperature. the offset voltage is measured as the signal. which shows up as zero and span drifts.Chapter 3 Catalytic Combustible Gas Sensors in a square.

shows the sensor bead. One way to improve stability of the sensor is to coat the platinum wire with suitable metal oxides. it is difficult to maintain its coil shape. Thus. such as platinum. This may also be achieved by coating platinum wire with a non-catalytic metal.Hazardous Gas Monitors gas. Therefore. The coating makes the sensor physically very rugged. such as gold. Also. palladium or thoria compounds. the coefficient of thermal resistance becomes less linear as the temperature increases. This is not practically possible. Another problem with hot platinum wire is that it becomes very soft at a temperature of 1000°C. A compromise is made by operating the reference wire at a temperature that is substantially lower so that no oxidation takes place in the presence of hydrocarbons. In addition. as well as a relatively short operating life. the final step is to treat the finished sensor or bead with a catalyst. Figure 4. PLATINUM WIRE CATALYTICALLY-TREATED METAL OXIDE Fig. This situation also results in poor zero and span quality of the sensor. The sensor becomes a very small 40 . however. 4 A Catalytic Bead Sensor The construction of the catalytic sensor bead is analogous to constructing a building by using reinforced concrete. the reference wire is chemically treated to reduce the catalytic property of the platinum.

The output is linear because the platinum wire has a good linear coefficient of thermal resistance. A near perfectly compensated pair of sensors is now possible. The sensor is called a “catalytic” sensor because the use of the catalyst is the main ingredient involved in the proper functioning of the sensor.Chapter 3 Catalytic Combustible Gas Sensors mass which helps make it resistant to shock and vibrations. or it is based on the theoretical combustion reaction formula. because finer wire has a higher magnitude of resistive value and the signal output is the percentage change of total wire resistance. Most importantly. and has a long operating life. 41 . The catalytic sensor is stable. This also reduces power consumption. Methane. accurate. assuming there is one part of oxygen and four parts of nitrogen in air. The bead can be further treated with chemicals. The reference sensor can be constructed in the same way as the active sensor. Characteristics The sensor’s output is directly in proportion to the rate of oxidation. The use of fine diameter wire not only reduces the size of the sensor. and rugged. for example: CH4 + 2O2 + 8N2 → CO2 + 2H2O + 8N2 It takes 10 moles of air for one mole of methane to complete the reaction. to prevent the reference bead from reacting with the gas. but it also increases the signal. with the exception that the catalyst chemical is eliminated. Therefore. The maximum output of the signal occurs at about the stoichiometric1 mixture of the gas. reliable. one part of methane will require 10 parts of air 1 Pertaining to substances that are in the exact proportions required for a given reaction. such as potassium. the catalyst coating reduces the temperature needed to achieve a stable signal for hydrocarbons between 400°C and 600oC. for a theoretical combustion to take place.

the signal increases very rapidly and peaks at around 10%. 5 Sensor Output vs. propane.09% of methane in a mixture of air. This value is near half of the theoretical combustion value. The signal starts to drop slowly as the concentration of gas passes approximately 20%. As the concentration reaches close to the stoichiometric value of 9%. illustrates this effect.Hazardous Gas Monitors to complete the combustion. the signal output will respond linearly from 0–5% of methane (which is 100%LEL). 3-5%: SLIGHTLY LESS LINEAR LEL 10 8 Sensor Output in volts UEL 6 4 2 0 5 10 15 20 40 60 80 100 % Methane Gas Concentration Fig. For a sensor to detect methane. after 20% it drops straight down to a level that reflects no output as the concentration of gas reaches 100%. Gas Concentration Consider another example. 42 . There is a safety factor of 2 added to ensure safety. 0-3%: NEARLINEAR.85%.1%. Figure 5. The LEL for methane is 5% and for propane is 2. or theoretically 9. The reaction formula for propane is: C3H8 + 5O2 + 20 N2 → 3CO2 +4H2O + 20N2 or one part of propane per 25 parts of air for theoretical combustion of propane. The actual theoretical combustion concentration for propane is 3.

3. The exact cause of this poisoning is very difficult to identify. excessive heat. These are just a few typical chemicals that inhibit the sensor performance and are by no means to be considered as the sole possible inhibitors. 2. Sensor Cracking: The sensor. 1. after 24 or 48 hours of exposure to ambient air. The most common chemicals that can poison catalytic sensors are those that contain silicon. when exposed to excessive concentration of gases. Sensor Inhibitors: Chemicals such as halogen compounds. Some chemicals. will totally destroy the sensor. There have been instances in which the silicon contained in simple hand lotions has caused problems with catalytic sensors. Sometimes this will change the zero and span setting of the sensor. Sulfur compounds. such as the common oil and lubricants with silicon compounds used as additives in machinery. with very small concentrations.Chapter 3 Catalytic Combustible Gas Sensors Sensor Operation Factors There are several factors affecting the operation of the catalytic sensor. the sensor starts to function normally. and heavy metals also cause the poisoning of the sensor. 4. may eventually deteriorate. Catalyst Poisoning: There are chemicals which will deactivate the sensor and cause the sensor to lose sensitivity and eventually become totally nonresponsive to gases. which are often released with gases. Correction Factors: Catalytic sensors are most 43 . and the various oxidation processes that take place on the sensor surface. chlorine. which are used in fire extinguishers and Freon used in refrigerants. will inhibit the catalytic sensor and cause it to temporarily lose the ability to function. Normally.

Furthermore. The manufacturers generally provide a set of correction factors that allow the user to measure different hydrocarbons by simply multiplying the reading by the appropriate correction factor to obtain the reading of a different gas. Ignition source This is sometimes referred to as the combustion triangle. But in real life. if the sensor is set to read butane. while the same sensor will only need 2. However. methane gas is a very common gas and is often encountered in many applications. In addition.3 volts for butane gas. Percent LEL for Mixtures of Hydrocarbons: For combustion to take place. The reason for using methane as the primary calibration gas is that methane has a saturated single bond that requires the sensor to operate at the highest temperature in comparison to other hydrocarbons. the process of igniting a combustible mixture is much more complicated. it will not read methane properly. The en44 . The correction factors can vary from sensor to sensor. and they can even change on the same sensor as the sensor ages. 5.Hazardous Gas Monitors Relative Sensitivity As an example for a typical sensor calibrated for 100% LEL methane gas. it is also easy to handle and has the ability to be mixed into different concentrations easily. Therefore. Combustible mixture b. Oxygen c. the following requirements must be present: a.5-volt bridge voltage to obtain a good signal. the best way to obtain precise readings for a specific gas is to actually calibrate the sensor to the gas of interest directly. Therefore. the relative sensitivity to other gases is as follows: Gas Methane Propane n-Butane n-Pentane n-Hexane Methanol Ethanol iso-Propyl Alcohol Acetone Methyl Ethyl Ketone Toluene Reading 100% 60% 60% 50% 45% 100% 70% 60% 60% 50% 45% commonly calibrated to methane for 0-100% LEL full scale range. a typical catalytic sensor for methane gas may require a 2. it should be noted that the correction factors are a set of numbers that should be used with great care. For instance.

Therefore. depending on the manufacturer and cable size used to wire the sensor.000-3. Therefore. This is a very common mistake made by many users of gas detection equipment. it is not even possible to calculate and determine the combustion range of the mixture. while infrared instruments will produce much higher readings if exposed to a higher carbon content gas. The overall technology of making a sensor for the market is more of an art than a predictable scientific event. if the unit is used for some other gas or mixture of gases. temperature. most users of catalytic sensors select their sensors based on the reputation of the manufacturer. 45 . a catalytic sensor calibrated on methane produces lower readings when exposed to hydrocarbons of higher carbon content. a sensor calibrated at a percentage LEL for one gas cannot necessarily be used for other gases. This is particularly true in selecting. Many instruments on the market today have a scale unit as a percentage of LEL without indicating that the unit is calibrated on methane. temperature of the ignition source. Typical Specifications for Catalytic Sensors Sensor Type: Diffusion catalytic bead Temperature Range: –40oC to +60oC Response Time: 10 to 15 sec. and even humidity can have an affect on the combustible mixture concentration. Therefore. to 90% of reading Accuracy: ±5% Repeatability: 2% Drift: 5–10% per year Life Expectancy: Up to 3 years.000 meters. such as pressure. Summary A catalytic sensor is relatively easy to manufacture. depending on application Sensors can be remotely mounted up to 2. it is best to consider the worst-case scenario and calibrate the sensor accordingly. the data can be totally meaningless. Furthermore. There are too many variables in the process that inhibit the making of a predictable final product. For example. If two or more chemicals are involved. However. the quality of the sensor varies quite drastically from one manufacturer to another. preparing and processing all the chemicals needed to make the final sensor.Chapter 3 Catalytic Combustible Gas Sensors vironmental conditions.

. International Sensor Technology (IST) in Irvine. such a behavior was considered a problem. California introduced a solid-state sensor for the detection of hydrogen sulfide in a range of 0-10 ppm. The intention was to provide an alternative to the popular catalytic bead sensor. which suffered from several problems. Subsequently.Chapter 4 Solid-State Gas Sensors Chapter 4 Solid-State Gas Sensors hen scientists were doing research work related to semiconductor p-n junctions. Taguchi marketed a simple semiconductor. unsuccessful attempts were made to utilize the sensitivity of the semiconductor junction as a gas detection device. This problem. 1 The positive and negative junctions in a semiconductor. was solved by encapsulating the semiconductor chip so that it was no longer exposed to the outside environment. however. At that time. N.1 they discovered that these junctions were sensitive to environmental background gases. A few years later. 1 A solid-state sensor used for detecting more than a hundred toxic gases. including loss of sensitivity with time due to poisoning and burning out when exposed to high gas concentrations. This was a significant development. It wasn’t until 1968 that Mr. IST developed solid-state sensors for the detection of more than 100 different hazardous gases at low ppm levels. In 1972. for the detection of hydrocarbons in LEL combustible ranges. since OSHA was being formed at about 47 W Fig. or a solid-state sensor.

It is not unusual to find fully functional sensors that were installed 30 years ago. For this huge market. Today. gas simply “adsorbs” onto the sensor surface. Principle of Operation A solid-state sensor consists of one or more metal 48 . solid-state sensors are available for the detection of more than 150 different gases. Because catalytic sensors burn the gas being detected. After a few years of usage. There are now several manufacturers of solid-state sensors. but each sensor has different characteristics and different manufacturers offer different levels of performance and quality. the catalytic sensors had become less popular for such applications due to the need for frequent sensor replacement. In the early 1980s. including sensors for the gases which could otherwise only be detected using expensive analytical instruments. With solid-state sensors.Hazardous Gas Monitors the same time and began to regulate acceptable gas concentration levels for safety at the workplace. When the gas disappears. Japan passed a law that required gas detectors to be installed in residential apartments where gas bottles were being used. the sensor returns to its original condition. solid-state sensors offer a very long life expectancy. While there were some initial complaints about solid-state sensors that produced false alarms. and hence the solid-state sensors offer a long life expectancy. the competition was between solid-state and catalytic bead sensors. No sensor material is consumed in the process. The Rise in Popular Use of Solid-State Sensors. sensor material is consumed and changed in the process and the sensor eventually burns out. changing the resistance of the sensor material. this was far outweighed by the long life the sensor provided. Properly manufactured. on the other hand.

which heats the metal oxide material to an operational temperature range that is optimal for the gas to be detected. There are different ways of making solid-state sensors. 2. A pair of biased electrodes are imbedded into the metal oxide to measure its conductivity change. in a fashion similar to making semiconductors. Schematic Diagram of a Bead-type Sensor 2. Two typical Control styles are the following: 1. In the presence of gas. Chip-type sensor (Figure 3. such as tin oxide. aluminum oxide. These metal oxides are prepared and processed into a paste which is used to form a bead-type sensor. Alternatively. especially at high gas conVOUT centrations. Bead-type sensor (Figure 2) Fig.Chapter 4 Solid-State Gas Sensors oxides from the transition metals. a resistive metal oxide. the metal oxide causes the gas to dissociate into charged ions or complexes which results in the transfer of electrons. Typically. The changes in the conductivity of the sensor resulting from the interaction with the gas molecules is measured as a signal. is regulated and controlled by a specific circuit. etc. next page) 49 . or a thin layer of deposited platinum. The sensor is then processed at a specific high temperature which determines the specific characteristics of the finished sensor. since the finished sensors exhibit different gas response characteristics at different temperature ranges. The builtin heater. Platinum Collector Coil Heater a solid-state sensor produces a ver y strong signal. thick or thin film-chip sensors are made when the metal oxides are vacuum deposited onto a silica chip. This heating element can be a platinum or platinum alloy wire. A heating element is used to regulate the sensor temperature. each arrangement making the sensor’s performance Heater characteristics different.

Thus. Versatility. Longevity. and sensor operating temperature. the interferences from other gases are minimized by using appropriate filtering materials that absorb all other gases except the gas to be detected. For example. which typically last only one to two years. as well as high combustible levels. 3 Characteristics Silicon Substrate Solid-state sensors are among the most versatile of all sensors. while solid-state sensors have a longer life expectancy. depending on how the heater and bias electrodes are connected. However. This is a major advantage compared to other sensor types. such as catalytic bead or electrochemical sensors. as the sensor typically lasts 10 years or more in clean applications. The versatility of the solid-state sensor 50 . and can be Chip-type Sensor used in many different applications. solid-state sensors may trigger false alarms. In certain instances. This way the sensor performs very well and becomes very selective for those two gases. Fig. they are also more susceptible to interference gases than the other types of sensors. in applications where other background gases are present.Hazardous Gas Monitors Collector Termination Termination Most solid-state sensors have three or four pins. processing techniques. The main strength of the solid-state sensor is its long life expectancy. as they deHeater Resistor tect a wide variety of gases. Different response characteristics are achieved by varying the semiconductor materials. a solid-state sensor for monitoring carbon monoxide and hydrogen can be equipped with a charcoal filter which eliminates the majority of interfering gases. Among the unique attributes of the solid-state sensor are the abilities of the sensor to detect both low ppm levels of gases.

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is one of its main advantages. For example, in chemical plants, a gas monitoring system may involve the monitoring of many different gases and ranges, or even the same gas with multiple ranges. Often, the lower ranges need to be monitored for certain gases for toxic concentrations while simultaneously, the same gas needs to be monitored in the combustible range for explosive concentrations. The solid-state sensor is capable of detecting gas in both ranges. This greatly simplifies the system design and maintenance required because it eliminates or minimizes the use of multiple sensor technologies which must be designed and maintained differently. A list of gases that are detectable by using IST’s solid-state sensors is shown in Table 1 (pages 52-53). The typical ppm ranges which are chosen are three to five times the permissible exposure limits for an eight-hour work day or ranges that can be based on the sensitivity as well as the interference characteristic of the sensor, whichever is the most practical in an application.

Typical Specifications for Solid-State Sensors*
Accuracy: ±3% to 10% of full scale Response Time: T 80 ranges from 20 seconds to 90 seconds Temperature Range: –20oC to +50oC Humidity: 5–9% Life Expectancy: 10+ years Power Consumption: Approx. 300mW *Actual specifications will vary depending on gas and range.

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Hazardous Gas Monitors

Table 1: IST’s Solid-State Sensors Gas List
GAS FULL-SCALE RANGE Low ppm or higher LEL GAS FULL-SCALE RANGE Low ppm or higher LEL

Acetic Acid Acetone Acetonitrile Acetylene Acrolein(Acrylaldehyde) Acrylic Acid Acrylonitrile Allyl Alcohol Allyl Chloride Ammonia Anisole Arsenic Pentafluoride Arsine Benzene Bophenyl Boron Trichloride Boron Triflluoride Bromine Butadiene Butane Butanol Butene Butyl Acetate Carbon Disulfide Carbon Monoxide Carbon Tetrachloride Cellosolve acetate Chlorine Chlorine Dioxide Chlorobutadiene Chloroethanol Chloroform Chlorotrifluoroethylene Cumene Cyanogen Chloride Cychlohexane Cyclopentane

100 100 100 50 50 100 50 —200 x50 100 5 1 50 50 500 500 20 50 400 1000 —100 50 50 50 100 10 10 —200 50 ——20 100 50

—yes —yes ——yes yes —yes ———yes yes ———yes yes yes yes yes —yes ————yes ——yes yes —yes —-

Deuterium Diborane Dibromoethane Dibutylamine Dichloroethane (EDC) Dichlorofluoroethane Dichloropentadiene Dichlorosilane Diesel Fuel Diethyl Benzene Diethyl Sulfide Difluorochloroethane Difluoroethane (152A) Dimethyl Ether Dimethylamine (DMA) Epichlorohydrin Ethane Ethanol Ethyl Acetate Ethyl Benzene Ethyl Chloride Ethyl Ether Ethylene Ethylene Oxide Fluorine Formaldehyde Freon-11 Freon-12 Freon-22 Freon-113 Freon-114 Freon-123 Fuel Oil or Kerosene Gasoline Germane Heptane Hexane

10 50 —50 100 50 50 50 —10 ———20 50 1000 200 200 200 100 100 100 5 20 15 1000 100 100 100 1000 1000 —100 10 1000 50

yes ——yes yes ———yes yes —yes yes yes ———yes yes yes yes yes yes yes ———————— yes yes —yes yes

52

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Table 1 (continued) : IST ’s Solid-State Sensors Gas List
GAS FULL-SCALE RANGE Low ppm or higher LEL GAS FULL-SCALE RANGE Low ppm or higher LEL

Hexane Hydrazine Hydrogen Hydrogen Bromide Hydrogen Chloride Hydrogen Cyanide Hydrogen Fluoride Hydrogen Sulfide Isobutane Isobutylene Isopentane Isoprene Isopropanol JP4 JP5 Methane Methanol Methyl Acetate Methyl Acrylate Methyl Bromide Methyl Butanol Methyl Cellosolve Methyl Chloride Methyl Ethyl Ketone Methyl Hydrazine Methyl Isobutyl Ketone Methyl Mercaptan Methyl Methacrylate Methyl-Tert Butyl Ether Methylene Chloride Mineral Spirits Monochlorobenzene Monoethylamine Morpholine Naptha Natural Gas

100 5 50 50 50 20 20 5 1000 —1000 —200 1000 1000 100 200 30 60 20 ——100 100 5 200 30 100 —20 200 —30 500 1000 1000

yes —yes ————yes yes yes —yes yes yes yes yes yes ———yes yes yes yes —yes —yes yes yes yes yes ——yes yes

Nitric Oxide Nitrogen Dioxide Nitrogen Trifluoride Nonane Pentane Perchloroethylene Phenol Phosgene Phosphine Phosphorus Oxychloride Picoline Propane Propylene Propylene Oxide Silane Silicon Tetrachloride Silicon Tetrafluoride Styrene Sulfur Dioxide Tetrahydrofuran Tetraline Toluene Toluene Diisocyanate Trichloroethane Trichloroethylene Triethylamine (TEA) Trifluoroethanol Trimethylamine (TMA) Tungsten Hexafluoride Turpentine Vinyl Acetate Vinyl Chloride Vinylidene Chloride Xylene

20 20 50 2000 200 200 100 50 3 200 —100 100 100 10 1000 1000 200 50 200 100 50 15 50 50 100 25 50 50 —1000 20 50 100

————yes —————yes yes yes yes ———yes —yes —yes ——yes ————yes yes yes ——-

53

With most sensor types. and expensive. 55 I Gas Cell Fig. 1 An example of an IR gas monitor with the gas cell assembly exposed. However.Chapter 5 Infrared Gas Sensors Chapter 5 Infrared Gas Sensors nfrared (IR) gas detection is a well-developed measurement technology. often causing the sensor to drift or die prematurely. and these demands will likely continue to nourish the advancement of this technology. have opened a new frontier for infrared gas analysis. Only the sample cell and related components are directly exposed to the gas sample stream. The main advantage of IR instruments is that the detector does not directly interact with the gas (or gases) to be detected. These advancements have resulted from an increase in demand in the commercial sector. making them resistant to corrosion. gas molecules interact only with a light beam. Today. many IR instruments are available for a wide variety of applications. recent technical advancements. cumbersome. Many of them offer simple. Gases to be detected are often corrosive and reactive. These components can be treated. In other words. . including the availability of powerful amplifiers and associated electronic components. The major functional components of the analyzer are protected with optical parts. and can be designed such that they are easily removable for maintenance or replacement. Infrared gas analyzers have a reputation for being complicated. the sensor itself is directly exposed to the gas.

Principle of Operation The infrared detection principle incorporates only a small portion of the very wide electromagnetic spectrum. Wave Number = 10 cm Fig. 2 A simple mechanical wave showing 10 waves per centimeter to illustrate the concept of the wave. 56 . with a special emphasis on instruments used for area air quality and safety applications. In general. one wave followed by another.Hazardous Gas Monitors rugged. Electromagnetic radiation travels at close to 3 x 108 m/sec and has a wave-like profile. The portion used is that which we can feel as heat.1 cm. with mechanical waves having a much longer wavelength. Let’s review the basic physics of electromagnetic radiation by defining the terminology involved with it. There are both electromagnetic and mechanical waves. from parts per million levels to 100 percent concentrations. Wave: Similar to a wave in the ocean. There is virtually an unlimited number of applications for which IR technology can be used. 1 cm 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 2 cm 20 1 sec 2 sec -1 Frequency = 10 Hz. IR instruments are among the most user friendly and require the least amount of maintenance. Figure 2 illustrates a mechanical wave. for toxic and combustible gas monitoring applications. Wavelength = 0. and reliable designs. Gases whose molecules consist of two or more dissimilar atoms absorb infrared radiation in a unique manner and are detectable using infrared techniques. This chapter provides general information. Infrared sensors are highly selective and offer a wide range of sensitivities. This is the region close to the visible region of the spectrum to which our eyes are sensitive. the electromagnetic radiation waves oscillate.

or the spacing between two waves. Mathematically. Used to describe the amount of energy absorbed by gas molecules. It is commonly expressed in microns. the frequency is the speed of light divided by the wavelength. The formula is: Wave number = 1/wavelength Micron: A common unit used to express wavelength in the infrared region. the reciprocal of one micron is 1/10-4 (10. Wave number and wavelength are common terms used by scientists to describe the infrared region for gas analysis because they provide a convenient method to express radiation frequency and the mechanisms of interaction between infrared radiation and gas molecules. It is one millionth of a meter(10-6m) or a micrometer. Since 1 micron = 10-6 m = 10-4 cm. It is a very popular term used in representing gas molecular absorption bands as well as optical component characteristics. Wave number: The number of waves in one centimeter. It is used to specify optical parts.Chapter 5 Infrared Gas Sensors Frequency: Number of waves per second passing through a point. or 3 x 108 m/sec. and is expressed as the number of waves per second. and is abbreviated as µ. they are the reciprocals of each 57 Reflected Energy 10 Incident Energy Absorbed Energy Transmitted Energy 100 25 65 Transmittance = 65 = 65% 100 . Wavelength: The distance between two peaks of the wave. and 2 microns = 5000 wave numbers per cm. Both percent absorption and percent transmittance are used as the y-axis versus wave number or wavelength as the x-axis in the infrared spectra.000 wave numbers per cm). It is the reciprocal of wavelength. Therefore. Absorbance: Opposite of transmittance. Transmittance: The ratio of transmitted radiation energy to the incident energy. or hertz (Hz). An electromagnetic wave travels at the speed of light which is 300 million meters per second. The energy not transmitted is absorbed and reflected.

or a wave number of 2941 cm-1.4µ. the more absorption bands that will occur. The complete range of frequencies of these waves is called the electromagnetic spectrum. infrared light. For example. ultraviolet light.Hazardous Gas Monitors Radio 10 6 Television 10 9 Microwave 10 12 Infrared Ultraviolet 10 15 X-rays 10 18 Gamma rays 10 20 4 x 1014 8 x 1014 Frequency (cycles/sec.4 to 0. The infrared region is most useful for gas analysis because absorption by gas molecules is unique and selective in this region. Gas molecules can be fingerprinted using their absorption characteristics and archived for 58 . They are classified from higher to lower frequencies as gamma rays. microwaves. shows a spectroscopic description of methane gas which illustrates that methane has a strong absorption peak at 3. at about 4 x 1014 Hz (or 0.7 microns). and radio waves. or a wave number of 2941 cm-1. and this explains why we feel. methane gas has the absorption wavelength of 3.) Electromagnetic waves propagate through space or matter by oscillating electric and magnetic fields. on page 59. and the specific character of the absorption curve is unique to each gas. is actually only a very narrow portion of the spectrum. The more atoms that form a molecule. In a vacuum. Visible light. Figure 3 shows the electromagnetic spectrum. temperature. The region in which this absorption occurs. These frequencies range from gamma rays of 1020 Hz to radio waves of 106 Hz. the amount of absorption. visible light. x-rays. 3 Location of Infrared in the Electromagnetic Spectrum other. (Figure 4. they travel at the speed of light. Infrared is just below visible light. but do not see.4 microns.) Fig.” The complexity of the gas molecules determines the number of absorption peaks. Unique Gas Absorption “Fingerprints.

A typical spectroscopy scan of methane is shown in Figure 4. the graph is then compared with the stored curves to identify the gas molecules. This method of gas analysis is the most popular in analytical chemistry. while carbon monoxide absorbs strongly at 4. Gas molecules are made up of a number of atoms bonded to one another. which is the wavelength used for methane detection. 4 A Spectroscopy Scan of Methane Gas gas analysis and identification purposes.Chapter 5 Infrared Gas Sensors METHANE CH4 CH4 Fig. only one specific absorption region is used to quantitatively determine the gas concentration. Natural Frequencies of Gas Molecules. This bonding vibrates with a fixed frequency called Hydrogen the natural frequency. These interatomic bonds are similar to Natural Frequency springs. Figure 5 illustrates water molecules with one oxygen and two hydrogen atoms.4 micron region. A library of these curves can then be stored in the memory inside an instrument.26 microns. The scan shows that methane gas has a strong absorption peak at 3. connecting atoms of various masses together. most common hydrocarbon gases have strong absorption in the 3. carbon dioxide is absorbed strongly at 4. On the other hand. In gas monitoring applications. 5 Water Molecule .7 microns. As a matter of fact. 59 Oxygen Hydrogen Fig. When a given gas is scanned by the instrument.000 to 670 cm-1. The wavelengths in this region are between 2 and 15 microns or wave numbers of 5.4 microns.

60 . This vibration results in a rise in the temperature of the gas molecules. People moving around a balcony generate vibrations of certain frequencies. the molecules gain energy and vibrate more vigorously. this can cause a much more violent vibration of very high amplitude.Hazardous Gas Monitors 1 0 1 Natural Frequency 2 1 0 1 2 External Resonant Wave 3 2 1 0 1 2 3 Resultant Wave Fig. Thus. and the balcony in a theater has a natural frequency. Even though these are mechanical waves. The larger the molecules. 6 Energy Absorption by Gas Molecules All matter has a natural frequency. as shown in Figure 6. Infrared radiation contains a wide spectral content. As the gas molecules absorb this radiation. This radiation energy decrease can be detected as a signal also. resulting in severe damage. Gas molecules have a number of natural frequencies. If the wind or an earthquake shakes a bridge at the same frequency as the bridge’s natural or resonant frequency. The particular properties exhibited by the chemical become its signature and offer clues to identify the molecular structure of the given chemical compounds. They are always the same for a given molecule and bonding structure. Two Ways of Detection. When this radiation interacts with gas molecules. the radiation absorbed by the gas molecules at the particular wavelength will cause a decrease in the original source strength. Natural frequencies are also determined by the molecular structure of the chemicals. part of the energy has the same frequency as the gas molecule’s natural frequency and it is absorbed while the rest of the radiation is transmitted. The Golden Gate bridge in San Francisco has a natural frequency. which can cause a similar effect. The temperature increases in proportion to gas concentration. the more modes of natural frequencies they have. in theory they are similar to electromagnetic waves. On the other hand. the natural frequency of a structure is a concern for structural engineers. and is detected by the detector.

1. Using techniques used in the semiconductor industry. there are no specific rules regarding the selection of each of the components. but offers the advantages of DC stability. The size and mass of the device are important in determining its response time and other characteristics of the device. This detector has a relatively slow response time. and responding to all wavelengths. Some of the types are described briefly below: a. Thermistor Bolometer: A bolometer changes resistance when incident infrared radiation interacts 61 THERMOCOUPLE Metal 1 – + Metal 2 T1 T2 Dissimilar Metal Junction T1 = Reference or normally ice point T2 = Measuring probe . requiring no bias. The junction of dissimilar metals generates a voltage potential. Following is a description of the major components.Chapter 5 Infrared Gas Sensors Key Components for Analysis To get a useful signal for gas analysis. There are many types of infrared detectors and each detector type offers a wide range of performance characteristics. which is directly proportional to the temperature. This junction can be made into multiple junctions to improve sensitivity. The configuration of these instruments depends on what needs to be accomplished and the discretion of the designer. yet the detector package is miniaturized and compact. Such a configuration is called a thermopile. Thermoelectric: A detector that converts temperature into an electrical signal is commonly known as a thermocouple. b. However. It is the simplest way of converting light energy into an electrical signal. Detector: Infrared detectors convert electromagnetic radiation energy or temperature changes into electrical signals. there are many different components and parts used in the various designs found today. many junctions are connected in a series to multiply the output of the device.

A photon that strikes an electron with sufficient energy can raise the electron from a nonconducting state into a conducting state. which exhibit spontaneous polarization.Hazardous Gas Monitors PYROELECTRIC Infrared Pyroelectric Crystal with the detector. As infrared radiation strikes the detector surface. and a bias voltage registers this change as a signal. and therefore more energy. A typical example of such detectors are lead sulfide (PbS) detectors used in the 1-3 micron region. It has a high temperature coefficient of resistance. c. Shorter wavelengths have higher frequencies. such as lithium tantalate. and does not require cooling of the detector. This detector exhibits good sensitivity and good response to a wide range of wavelengths. Photon Detector: Photons possess energy based on their wavelength and intensity. which depends on the detector material being used. This thermally sensitive semiconductor is made of a sintered metal oxide material. and lead selenide (PbSe) detectors used in the 1-5 micron region. This current is proportional to the intensity of the radiation. d. 62 . Pyroelectric Detector: Pyroelectric materials are crystals. Typically. or a concentrated electric charge that is temperature dependent. the detector must be cooled with a thermoelectric cooler or even liquid nitrogen for it to function properly. It is the most commonly used detector for gas monitors. The presence of electrons in the conduction band will increase the conductivity of the chip. A photon detector detects the quantum interaction between incident photons and semiconductor material. This detector functions in a limited spectral region. the change in temperature causes a current to flow. The excitation of electrons requires photons to have a certain amount of energy.

The chambers are sealed with a target gas at a low pressure. In the case where a diaphragm separates the two chambers. Photoacoustic Detector: This detector is similar to the luft detector except that the pressure change is measured by a condenser microphone. The pulsating pressure change is measured by the microphone as a frequency change which produces the signal.” and the original luft detectors were designed in Germany. 63 LUFT IR Source Chopper Sample Out Motor SAMPLE CELL Sample In REFERENCE CELL IR-Transparent Window Reference Chamber Detector Chamber Micro-Flow Sensor or Diaphragm PHOTOACOUSTIC Infrared Microphone . f. IR transparent windows are fitted to seal the chambers and the same intensity of pulsed infrared radiation is received by both chambers when no target gas is present. The sample gas is passed through a chamber at a preset time interval and the chamber is sealed with a fixed volume of sample gas trapped inside. the pressure difference between the two chambers causes a detectable flow. and has good potential for further development. This detector finds many useful applications as an analyzer. Luft Detector: The word “luft” is a German word meaning “air. a reduction in radiation energy is received by the detector chamber. A specific wavelength of infrared radiation is pulsed into the chamber via an infrared transparent window. which causes the temperature and pressure to drop in the detector chamber. The amount of temperature or pressure drop is in direct proportion to the gas concentration. 2. A heated wire filament. A luft detector consists of two chambers. When the sample containing target gas flows through the sample cell. a movement of the diaphragm causes a measurable change in capacitance.Chapter 5 Infrared Gas Sensors e. which is measured as a signal. Infrared Source: A regular incandescent light bulb is a good infrared source. In the case of linked chambers. either linked by a micro flow sensor or divided by a diaphragm.

The pulsating filament source typically provides a wavelength in the range of 2-5 microns. creating a pulsing frequency. which resembles a fan blade. The difference between the two is the way in which the spe64 . carbon dioxide. in order for the detector and corresponding circuitry to function properly. Optical filter: There are two basic types of gas analyzers. turning it on and off at a specific frequency.Hazardous Gas Monitors similar to that in a pen flashlight. it may be necessary to modulate the light source. There are many light sources available. depending on the filament temperature and bulb enclosure material. The blade interrupts the light. This simple and inexpensive light source offers long life and long-term stability. 3. The advantage of the chopper is that it is simple and can provide a high chopping frequency. the large size of the chopper and motor assembly can be a liability for applications that require a simple. This is due to the fact that the filament is a heated wire and is limited to how fast it can be heated up and cooled down. one which would otherwise be unattainable by a pulsing filament source. The frequency is determined by the speed of the motor and arrangement of the chopper blade. Modulating the light. Typically. rugged instrument for use in harsh locations. this is done by passing the light through a chopper blade. namely dispersive and nondispersive. Depending on the type of detector used. ranging from specially designed heating filaments to electronically generated sources. There are many different light sources and modulating techniques available. Any source that can generate enough radiation at the wavelength of interest for the purpose of detecting the specific target gas may be used. pulsing filament sources are used whenever possible. Although choppers do have advantages. radiates sufficient energy in the 1-5 micron range for the detection of most hydrocarbons. and carbon monoxide. For this reason.

0 3. Typical specifications for a methane filter are shown in Figure 7. The filters are generally produced by a specialty optical manufacturer.2 3.6 Wavelength (µm) 3.3 3.0 Fig.8 3.Chapter 5 Infrared Gas Sensors cific wavelength of interest is extracted from the infrared source.1 3.5 3.7 3. 7 Methane Filter Specifications 65 . Nondispersive types use discrete optical bandpass filters. The dispersive type instrument is typically used only for special requirements. Almost all commercial IR instruments are of the nondispersive type. Percent transmittance specifies the ratio of transmit100% Peak Wavelength 80% Peak Transmission Transmittance 60% Transmission Region 40% Bandwidth Center Wavelength 20% 0% 3. The bandpass filter is one of the most important components in designing for the type of target gas and selectivity of an analyzer. This type of configuration is commonly referred to as nondispersive infrared (NDIR). Dispersive types utilize an optical device such as a grating or prism to spread the light spectrum over an area containing the wavelength of interest. similar to sunglasses that are used for eye protection to filter out unwanted UV radiation.9 4.4 3.

For applications that require high sensitivity. There Sample Gas Entrance/Exit are “inlet” and “outlet” ports that allow the sample gas to circulate through the tube. For applications where the selectivity and 66 . and stability. Gas Cell/Light Path: Gas cells are often designed in such a way as to allow the light path to interact with the sample gas. 4. A longer path length results in a greater signal using the same amount of radiation. The path length. where it meets the detector. The design may be relatively simple. By exposing the gas mixture to different filters. or very complicated. it is desirable to construct them using chemically inert materials to ensure the long-term stability and reliability of the instrument. This length is in direct proportion to the amount of radiation absorbed. selectivity. is called the length of IR Source Detector the gas cell. Configuration There are a number of ways by which various IR components can be arranged to produce a gas analyzer. different gases in the gas mixture can be identified. and hence the selectivity of the instrument. using many different optical components depending on the type of analyzers for the applications. There are certain designs where filters of different wavelengths are mounted in a carousal arrangement. Center wavelength determines the gas that will be detected. the longer the path length. or the distance in which the light passes through the gas. that is. This is normally done by using a tube that allows light to enter from one end and SELF-SAMPLING GAS CELL exit the other. the more radiation will be absorbed. the design of the analyzer is more complex. Bandwidth determines the selectivity of the filter. Since the gas cells are in direct contact with the gas sample.Hazardous Gas Monitors ted radiation to the incident radiation. Bandwidth is defined as the range of wavelengths that pass through the filter at half of the peak transmission point.

The active detector Filter/Detector has a filter for the target Fig. the reference detector provides a base point value or zero point while the active detector is used to provide the signal. and 10 illustrate some of the basic features of an IR analyzer. Modulated IR Source flashing IR sources are reflected back to the detecReference tors. the bandpass filter could be placed in front of the light source. The two-detector arrangement minimizes this type of drift. Figure 9 shows a similar Active layout except that two deFilter/Detector tectors are used. a simpler design can be implemented.Chapter 5 Infrared Gas Sensors sensitivity can be compromised for reliSample In Sample Out ability in a hostile. Figures 8. which will create a zero drift. while the reference detector has a filter with a different wavelength. (2) bandpass filter. in this arrangement. IR Source Filter Figure 8 shows a basic layout of: (1) Detector an IR source. and (3) Fig. 9 A Two-Detector Layout gas. In actual operation. In other words. For instance. This design uses two tubes or cells. the path length is doubled which leads to higher signal strength. Depending on the detector used. 8 A Basic Infrared Gas Detector Layout the interaction with the gas sample and detector. instead of placing it in front of the detector. Figure 10 illustrates another popular design. industrial environment. Also. the active detector is used to detect the target gas and the reference detector is used to ignore the target gas. with the differential between the two detectors providing the actual span value of the instrument. 9. This arrangement offers the advantage of compensating for the changes that occur in the detector’s sensitivity with time. the intensity of the light source can change with time due to contamination. One is a reference cell 67 MIRROR .

Water vapor condensation at the optics and/or on the detector can seriously affect the 68 . Generally. Most detectors do not react well to sudden temperature variations. which is basically a disc with a number of slots in it. potentially very sensitive to changes in the ambient temperature. a properly designed detector can be operated between -40°C to 60°C without being susceptible to ambient temperature fluctuations. this usually is not a serious problem because the ambient temperature changes only slowly. therefore. However.Hazardous Gas Monitors Chopper Motor MIRROR Sample In Sample Out Filter/Detector SAMPLE CELL MIRROR REFERENCE CELL IR Source Fig. similar to the reference detector in Figure 9. For outdoor applications. the detector unit is operated at a temperature slightly above the surrounding temperature to prevent condensation. while the other is a sampling cell in which the sample gas passes through. The instrument typically requires 10 to 20 minutes to achieve temperature equilibrium. As the chopper rotates. The gas signal is acquired from the sample cell. Characteristics 1. Temperature: An IR detector is essentially a temperature sensor and is. A chopper is used in this configuration. it alternately allows the light beam to pass through the sample and reference cells. The single detector gets its base reading from the reference cell. 10 Double Beams with Chopper Layout that is filled with a pure target or reference gas.

Life Expectancy: The IR detector is a solid-state device that is sealed inside a standard electronic package with a sapphire window filter. or drainage sumps. For some extremely “wet” applications. High humidity poses an even more serious problem in the presence of corrosive gases. the IR unit requires some means to linearize the output. However. however. The most common materials used are stainless steel. An example of the drastic difference between the sensitivity among varying hydrocarbons can be seen by the fact that an IR detector can be calibrated to 100% pure methane. the volume concentration of each gas to reach 100% LFL or LEL varies. but only a few percent by volume of propane or butane will saturate the system. For example. high humidity could promote corrosion and contamination that lead to the failure of the analyzer. the detector is least sensitive to methane (CH4) with its simple. hence.Chapter 5 Infrared Gas Sensors performance of the analyzer. each hydrocarbon must have its own curve programmed into the system. It has a long life expectancy. or copper. such as a confined space. 4. and the response curves are nonlinear. 2. The IR light source typically has a life expectancy on the order of 3 to 69 . The wave path (sample chamber) can be constructed of any material that does not absorb the IR light. single bond. In the case of percent lower explosive limit (%LEL) or lower flammable limit (LFL) applications. 3. Unlike the catalytic sensor. wet containers. the wet sample should be “dried” before exposing it to the detector. the sensitivity increases dramatically. With propane (C3H8) and butane (C4H10). similar to most electronic devices. Humidity: Normal environmental humidity has very little effect. plated with a corrosion-resistant coating. which has near linear response to gases at the LFL range. Sensitivity: The IR energy absorption is directly proportional to the molecular structure of the hydrocarbon (in addition to the concentration of the hydrocarbon present). aluminum.

Application As shown in Figure 11. 11 Advantage of an IR Detector. the IR source can be designed so that it can be easily replaced when needed. This lifetime can be dramatically prolonged by operating the source at a lower-than-designed energy. . Sampling should be done by diffusion. Carbon dioxide absorbs infrared radiation very strongly. 70 Span 0 Gas Concentration Fig. Once the zero point is established and maintained.1% and higher. as long as the zero point is maintained. However. This is due to the fact that the absorption of radiation by the gas is always in the same proportion. regardless of its initial source intensity. For gas monitoring applications. a routine calibration check is an invaluable safety check and should not be eliminated from any periodic maintenance.4 microns. Zero point has the highest output making it easy to detect any abnormal condition. which is considered the “zero” point for the source. the accuracy of the detector remains intact. The extractive type methods that require a pump to move the sample into the detector are more troublesome due to the limited electrical motor life expectancy and the maintenance required on the pump. Alternatively. This is the wavelength of most hydrocarbons and it is also where most of the hydrocarbon derivative gases have a strong absorption. With the filter used for the %LEL combustible gases application.Hazardous Gas Monitors Signal Zero 5 years. This is one of the biggest advantages of IR technology. the center wavelength is typically at 3. and many monitors are available that can detect carbon dioxide in concentration ranges of 0. The IR instruments used for this monitoring application are typically limited to the detection of higher concentrations (1% and above) of hydrocarbons and carbon monoxide. Therefore. the IR detector responds to radiation by generating a constant signal. the design of the unit should be relatively compact. the span calibration is automatically taken care of.

Aldehydes that have a central wavelength mostly at the 3. because of the many design options. methylvinyl ether. pentanone. 2. ethyl ether.Chapter 5 Infrared Gas Sensors Following is a list of common gases that are detected by this detector: 1. cyclohexane. Cycloalkenes such as cyclohexene and pinene. n-propyl ether. propanol. and pyridines. Carbon dioxide at 4. etc. 8. methyl isobutyl ketone and heptanone. Acetylene has absorption at 3. including the petrochemical industry. Ethers such as dimethyl ether. butane. Alkanes or saturated hydrocarbons such as methane. ethylene oxide. IR detection has been well received by many industries. For the purpose of area air quality and safety applica71 . However.6 microns have very little interference by other gases. Cycloalkanes such as cyclopropane. 5. Amines such as dimethyl amine. Nevertheless. furan. Alcohols such as methanol.1 microns which is not detectable. 4. 3. vinyl ether. octene.55 micron region and generally have a weak detection signal at 3. ethane. Ketones such as acetone. tetrahydrofuran. methyl cyclohexane. pentane. toluene. methyl ethyl ketone.4-dioxane. Aromatics such as benzene. ethanol. butene. etc. hexane. and allyl alcohol. and 1. and heptane. cyclopropanamine. etc.4 microns. hexene. the features and implementation of the technology vary greatly from one manufacturer to another. and xylene. trimethyl amine. 7.3 microns and carbon monoxide at 4. 9. 6. 10. butanamine. propylene. pentene. propane. Alkenes or unsaturated hydrocarbons such as ethylene. Summary Detection of hydrocarbons using IR has been available for a few years.

However. Life Expectancy: Catalytic sensors have a life expectancy of about 1-2 years. among others. one can tailor a solution to almost any hydrocarbon detection application. on IR units. IR instruments can be used to monitor a gas stream continuously over a long period of time. Poisoning: This is the main problem with catalytic sensors. Again. and catalytic bead sensors. 72 . as long as the zero is maintained. IR detectors do not suffer from this problem. which are basically inert to most chemicals. Burn Out: Catalytic senors will burn out if exposed to high gas concentrations. Only the IR radiation interacts with the gas. 3.Hazardous Gas Monitors tions. A well-designed IR unit also has a life expectancy of more than 10 years. solid-state. the functional components are protected by the optical parts. Continuous Exposure to Gas: In applications that require the detector to be constantly exposed to a gas stream to monitor for hydrocarbons. abnormal functioning of an IR unit can be easily determined. solid-state. Various chemical compounds. the IR unit is assured a good response and good span accuracy. as long as gas samples are dry and noncorrosive. catalytic and solid-state sensors will experience a shortened life span. IR detectors do not have this problem. can poison the catalyst in the sensor and cause the sensor to lose sensitivity. such as hydrogen sulfide. 5. 4. with IR instruments. used for the detection of combustible gases are given below. By selecting one of the three available sensor technologies (IR. and chlorinated or fluorinated compounds. 2. silicon compounds. Because of this characteristic. Continuous exposure to gas ultimately changes the characteristic of the sensor and leads to permanent damage. Calibration: Periodic calibration must be done on all sensor types. therefore. while solid-state sensors typically last more than 10 years. However. some comparisons between IR. 1. and catalytic).

which required monitoring of VOCs. 1 A Pocket PID Monitor . requirements for the monitoring of underground storage tanks to help prevent ground water contamination began to emerge. and is commonly employed in the detection of volatile organic compounds (VOCs). The lamps used today do not contain electrodes and are both less costly and have a longer life expectancy. In the 1980s.Chapter 6 Photoionization Detectors Chapter 6 Photoionization Detectors T he photoionization detector (PID) utilizes ultraviolet light to ionize gas molecules. These events led to the design of small. Early versions of this lamp used electrodes inside the lamp similar to those used in the early days of the vacuum tube and were quite costly to manufacture. and which offer fast response and the ability to detect low gas concentrations. which is essentially a lamp. Additionally. The heart of the photoionization detector is an ultraviolet source. the electronics that were designed were better able to process the small signal from PID sensors into useful and reliable data. portable PIDs (see Figure 1) that have proven to be both practical and reliable. To this 73 Fig. with the advent of integrated circuit (IC) technology. but its complexity limited its use elsewhere. This technique originally found use in bench top laboratory instruments.

Many different techniques are employed to power the PID lamp. [An electron volt equals 1. This 10.Hazardous Gas Monitors day. are much shorter than IR wavelengths.6 meters. when excited. A high voltage is required for the lamp 74 1 eV = energy gained when a particle of one electronic charge is accelerated through a potential of one volt. The radiant energy only changes in “quanta” or discrete steps. The wavelengths of infrared light used for gas analysis are in the micron region. or the equivalent of 10 eV and 10. or eV. Various other gases are also used.6 eV lamp happens to be the most popular lamp currently used in PID instruments. and hence more energy. Figure 2 on the following page shows wavelengths emitted by argon. krypton.2395 x 10-6/wavelength (ηm). depending on the manufacturer. The heart of the detector is the PID lamp which has an exterior shape resembling a medical ampule and comes in different sizes and dimensions. krypton.135 x 10-5 eV.] The PID Lamp. 10.6 eV. UV wavelengths. UV radiation has more energy than IR radiation. The wavelength of the UV light emitted depends on the type of gas in the lamp. being in the nanometer (ηm = 10-9 meters) region. 2 . an ultraviolet spectral radiation is produced. The lamp is filled with a low-pressure inert gas.9 ηm and 116. and xenon. For instance.9 ηm radiation.1 Wavelength is related to eV through Planck’s Constant2 which is 4. The term eV is used for convenience. PID sensors are the preferred choice for the detection of VOCs. Principle of Operation Ultraviolet (UV) light is the radiation group that has frequencies that are higher and are directly above visible light in the electromagnetic radiation spectrum. When this gas is energized with energy in resonance with the natural frequency of the gas molecules. Because shorter wavelengths have higher frequencies. UV radiation energy levels are commonly described in terms of electron volts. Planck’s Constant is a fundamental constant in quantum physics. will emit 123. to give a simple numerical expression of the radiant strength.

to function.Chapter 6 Photoionization Detectors XENON 147.9ηm 129.4eV 9. These types of lamps look similar to the vacuum tubes used in the early days of radio and TV. making the design of the portable instrumentation very compact. Although this type of lamp is used in many laboratories. the only way to excite the 75 . This lamp is only filled with a low-pressure inert gas and there are no electrodes inside the lamp. While the voltage used is in excess of 1000 volts.6eV 10. There are electrical terminations on the tube. The source needs to remain stable over time and also be efficient. a more popular lamp in use today is the electrodeless lamp.6ηm KRYPTON 123. Because there are no electrodes that provide power directly to the gas. and xenon. The Electrodeless Lamp.7eV Fig. krypton.9ηm ARGON 105. the current is very low. the low-pressure inert gas is separated by the lamp wall from the outside world. so as not to consume too much power. The simplicity of this design allows the lamp to be miniaturized. A typical design would place electrodes inside the lamp. and the gas discharge is confined to a small capillary.6eV 11.9ηm 116. 2 The wavelengths (ηm) emitted by argon. As a result.0eV 10.1ηm 8. In the electrodeless lamp. it is quite expensive.

and the energy applied is sufficient to excite the low-pressure gas inside the lamp. At the wavelength of radiation. There are several different ways this can be accomplished. low-current charge is applied to the electrodes. Therefore. and require special care and handling. 3 A Typical Photoionization Detector Configuration 76 . use argon gas and lithium fluoride windows. is to place a pair of electrodes on the exterior wall of the lamp. Gas Molecules Signal i + Insulation Window Electrode - V Electrode Plate for Lamp Illumination Lamp Fig. 10. most materials will absorb the radiation and prevent the transmission of such radiation. which have more energy. while 11.7 eV lamps. They are quite expensive. however. For instance. This window material is a crystal that allows good transmission of the targeted UV wavelength. Special Window Materials. A more popular technique. Figure 3 illustrates typical PID design. meaning the wave frequency of UV light. except on a much smaller scale. One method is to use electromagnetic radiation. These windows are soft glass and are very fragile. special window materials are placed at the discharge end of the lamp which allow spectral emissions to pass through.Hazardous Gas Monitors gas molecules is to use radiation energy that can penetrate the lamp wall. The design is similar to that of a fluorescent light used in a home or office. A high-voltage.6 eV lamps commonly use krypton gas and magnesium fluoride windows.

Gases detected between 9.5 eV and 10. Gases detected between 10. The ionization potentials for many gases are included in Appendix II at the end of this book. and 11. 2. On the other hand.Chapter 6 Photoionization Detectors A pair of electrode plates are placed in close proximity to the lamp window where the light is emitted. Distinct Ionization Potentials. 3. and the lamp is easy to clean. For most portable instruments. acetone.7 eV such as acetylene. they are ionized and the free electrons are collected at the electrodes resulting in a current flow whose magnitude is directly proportional to the gas concentration.7 eV lamp. Gases with IP values below the eV output of the lamp will be detected. Interchanging lamps in an unknown air sample helps to separate it into groups of gases.6 eV and 11. if one uses an 11.5 eV lamp such as benzene. As gas molecules move into the radiated field in the space between the electrodes. including 10 eV.6 eV lamp is most widely used because it detects most volatile organic compounds. formaldehyde.7 eV will be ionized. ethanol.5 eV. methanol. Most manufacturers design instruments with a lamp chamber that allows easy interchange of lamps. aromatic compounds.5 eV and will not ionize gases with higher ionization potentials. Each gas has its own unique ionization potential (IP). 8. The electrodes are biased with a stable DC voltage which will generate signals in case any small changes in the electrical field occur. Gases detected by 9. other lamps are also available. 9. However. amines. A 9. gases with ionization potentials up to 11. Following are examples of gases detectable using different lamps: 1.5 eV lamp will ionize gases with ionization potentials below 9.7 eV lamps.4 eV.6 eV such as ammonia. 77 . the 10.

For ammonia. it is necessary to individually calibrate the gas of interest. these factors can even vary somewhat from lamp to lamp. Instrument manufacturers typically supply a list of correction factors with their product. allowing calibration bottles to provide many calibrations. This gas is easy to handle and can be stored at high pressure. They will respond to all gases that have ionization potentials equal to or less than the eV output of their lamps. from those results obtained when one uses air as the balance. it is important to use 78 . In fact. Thus. and most of these gases are normally liquid solvents or other gases that are not easy to calibrate. for the most accurate readings on specific gases. Readings for other gases are obtained by multiplying the reading by a correction factor. a stable gas with a slightly pungent odor. PID instruments are very sensitive to the composition of gases in the sample. and data can be slightly different from manufacturer to manufacturer. Thus.Hazardous Gas Monitors Characteristics PID sensors offer fast response for detection of many volatile organic compounds. and the results may vary depending on the quality of the UV output of the lamp at the time of measurement. The results will differ vastly if one uses gas with dry nitrogen as the balance to calibrate. benzene has a correction factor of 0. For example. it is much easier to calibrate these instruments using isobutylene as the calibration gas.5. Correction Factor. Therefore. PID instruments typically detect gases at low concentrations. which means that a reading of 100 ppm isobutylene on the sensor indicates a concentration of 50 ppm benzene. which has a response factor of 10. An important point to remember is that correction factors are not absolute. a reading of 100 ppm on the sensor would indicate an ammonia concentration of 1000 ppm. PIDs are typically calibrated with isobutylene.

it does not exactly duplicate environmental air. resulting in a lower output reading. when compared to dry air. This is known as the “quenching effect.Chapter 6 Photoionization Detectors isobutylene in air as the calibration gas when the instrument is used for area air quality and safety applications. In dry nitrogen. and although the lamp radiant energy will not ionize these gas molecules. The output of the 2 PID sensor is relatively lin1 ear below 200 ppm. If the sample gas constituents include gas components that are ionizable but the ionization potentials are above the detecting lamp output potential. such “quenching” gases are water vapor. Generally. there will be some error because the calibration mixture is under high pressure and is dry. ambient air is. Zeroing Instruments for Best Results. etc. The common practice of calibrating the instruments with isobutylene in an air mixture. 5. therefore. readings are typically 10-30% higher than in dry air.” For example. results in an inaccurate reading. and 6 illustrate Fig. therefore. Thus. in environmental air. methane. clean air. dry. without making corrections. carbon monoxide. carbon dioxide. high humidity decreases the response by up to 30%. and environmentally clean air. 3 PID Response Characteristics. 4 Zero-to-200 ppm Curve Output Voltage 150 200 79 . Clean. This is another reason why a representative air is needed to zero the sensor and prepare the calibration gas mixture. Concentration Isobutylene Figures 4. PID sensors will exhibit different zero readings when exposed to nitrogen. the UV rays can be scattered and absorbed. the best choice for zero air 5 as well as for mixing cali4 bration gas. Still. it is best to zero the sensor in the same type of conditions that are present in the application in which it will be used. and the 0 detector output becomes 0 50 100 saturated above 2000 ppm.

The frequency of cleaning needed for the window depends on the sample stream conditions. 10. Thus. you can see that the detector becomes saturated. 6 Zero-to-4000 ppm Curve for detection of low ppm volatile organic compounds (VOCs). which sample continuously. and good sensitivity Fig. The additional 1000 ppm produces only 1. Generally.6 volts and 2000 ppm produces an output of 4. this output region does not provide a reading with a good resolution. they are not practical choices for use in stationary monitors. and 4000 ppm isobutylene in room air.Hazardous Gas Monitors 5 Output Voltage 4 3 2 1 0 0 500 1000 Concentration Isobutylene Fig. while on the 2000 1500 2000 ppm curve. Applications PID instruments offer ver y fast re0 1000 2000 3000 4000 Isobutylene Concentration (PPM) sponse. high accuracy. 5 Zero-to-2000 ppm Curve 500 Output Voltage (mV) 400 300 200 100 0 the response curves for 200 ppm. Lamp Life Expectancy. You will notice that the 200 ppm curve is relatively linear. Because the lamp window is directly exposed to the sample stream. The life expectancy of the lamp depends on the type of lamp. the condition of the window is very critical to accurate readings. and a dirty window will produce much different results than a clean window. or one third of the initial 1000 ppm.8 volts. The major shortcoming of these instruments is that the PID lamp requires frequent cleaning. 1000 ppm produces an output of 3.2 volts.6 eV lamps have the longest life expectancy. Because PID sensors require periodic cleaning and have limited life expectancies. 2000 ppm. From the 4000 ppm curve. Their use is limited to portable models in which only periodic readings are required. approximately 80 .

Response Time: 3 secs. Typical Specifications for PID Instruments Detector: 10. depending on range. Temperature Range: –20oC to +50oC.7 eV lamp optional. Thus. 81 . noncondensing.7 eV lamps have lithium fluoride windows that transmit the shorter UV wavelength light at 11. which allows for the detection of many more gases when compared to lower eV lamps.7 eV lamps are not typically used for general applications. Ranges: 100 ppm. Humidity: 0–95% relative humidity. Accuracy: 1-10%.1 ppm isobutylene. causing the window to degrade. Sensitivity: 0. which results in less stable and more temperature-sensitive instruments. the intensity of the light they emit is weaker than the light emitted from lower eV lamps. auto-ranging. 11. a special.7 eV. to 90% reading. 11. The 11. The weaker energy emitted means less signal. and 2000 ppm isobutylene equivalent. which means that lithium fluoride crystals attract and absorb moisture from the air. fine solid aluminum oxide powder is needed to clean the lamp. They also cannot be exposed to cleaning solvents because most solvents contain small amounts of water. However. 1000 ppm.Chapter 6 Photoionization Detectors 6000 hours. lithium fluoride is hygroscopic.6 eV electrodeless discharge lamp. Therefore. Furthermore.

Electrochemical Analyzer Type: UV Photometers UV Fluorescence Chemiluminescence Flame Ionization Infrared Catalytic Combustible Gases Solid-State Infrared Volatile Organic Compounds Photoionization Total HydroCarbons Flame Ionization MultiGas (Laboratory) Most UV/IR Absorbing Gases Most IR Absorbing Gases Most Gases UV/IR Spectrometer Fourier Transform IR Mass Spectrometer Gas Chromatograph Other Gases Thermal Conductivity Colorimetric *Total hydrocarbon . Zirconium Oxide.Hazardous Gas Monitors Sensor Selection Overview Application Requirement • Safety Monitoring (LEL) • Toxic Limit Detection (PEL) • Leak Detection • Personal Safety LIMIT DETECTION ALARM • Exposure Assessment (TWA) • Ambient Air Quality Compliance Monitoring QUALITATIVE & QUANTITATIVE ANALYSIS Monitors Monitor Type: Toxic Gases Electrochemical Solid-State Analyzers Target Gas: O3 SO2 Air Quality Monitor Single Gas (Online) Continuous Emission Monitor NOx THC* CO CO2 SO2 O2 Paramagnetic.

They should be safe for use in industrial environments. The sensor should be suitable for use in hazardous locations and harsh environments. For portable applications. The instruments should be small and portable so they can be carried easily. preferably longer than 30 days. The sensor should be cost-effective. the instruments should have reasonable energy consumption and the option of powering the instruments with batteries should be easily available. Preferably. 3.Chapter 8 Sensor Selection Guide Chapter 8 Sensor Selection Guide ach of the following sensors—electrochemical. designed for installation and use in industrial production areas. the instruments should be certified as intrinsically safe for use in a hazardous area. In stationary installations. and. Some of the basic requirements are: 1. and installable at a reasonable cost. it should also be explosion-proof. the sensors should be able to function continuously and reliably for a period of time. The sensor should be designed for a housing that is small and rugged. 2. 4. The sensor E 103 . The operation and maintenance of the instruments should be easily performed by regular plant personnel with minimal special training requirements. solid state. catalytic bead. infrared and photoionization detectors—must meet certain criteria to be practical for use in area air quality and safety applications.

5. For example. There are other types of sensors which meet the above criteria. Factors to Consider When Selecting Sensors One of the most frequently asked questions regarding sensors is: “Which sensor is the best?” Of course. Four of the five sensors discussed in this book all meet the above criteria. to choose the correct sensor. However. there is no simple answer to this question. The PID is a good detector for portable applications but is limited by the lamp because it has a relatively short life expectancy and the frequency of maintenance required may not be practical for stationary applications. 104 . Thus. The illustration on page 102 shows an overview of various application requirements and their detection technologies. one must first properly define the application. and thus the suitability of a given sensor depends largely on the application in which it is to be used. thermal conductivity sensors are mostly used for high concentration applications and are not widely used as gas monitors. The exception is the photoionization detector. Each sensor has certain capabilities and limitations. but most have limitations. It should be easy to install into a multi-point system and be managed by a controller or a computer controlled distribution system. there are PID stationary instruments available that can be useful as long as users are aware of the limitation.Hazardous Gas Monitors should be able to function in an industrial environment for at least two years or longer and should be replaceable or renewable at a reasonable cost. The cost of the instruments should be reasonable so that multiple sensors can be installed to effectively protect the area. It is common for manufacturers to exaggerate the capabilities of the sensors that they offer and downplay sensors that they do not offer.

it is more appropriate to measure in ppm ranges. C. The ranges or the concentration of the gases to be measured should be 3 to 5 times the actual monitoring concentration. and during summer and winter. The selectivity or specificity of the sensor must be acceptable for the application. The temperature ranges in which the sensor is to be installed should be within the sensor specifications and should be suitable for the gases to be monitored. B. Realistically define what objective one is trying to accomplish and define an instrument specification that meets the minimum requirements. A major cause of sensor failure is the presence of background gases that the instrument’s manufacturers did not take into consideration. the following factors/observations should be considered: A. A wide temperature change 105 . Determine the background gases in the monitoring area. As with a voltmeter. The temperature changes between day and night. It is useless to install a sensor to measure the combustible range in a hangar if the temperature will never exceed 100° F because the vapor concentration cannot reach combustible levels. For example. one should always select a range higher than the actual voltage to be measured. jet engine fuels have very low vapor pressure. In this example. In cases where the background gases cannot be determined. a representative sample should be analyzed. should also be considered. The specifications should define the gases and ranges of the sensors.Chapter 8 Sensor Selection Guide In determining which sensor to use for a given application. select a 50-volt range to measure a 12-volt battery. For example.

Both solid-state and catalytic sensors have heated elements. In this case. The occurrence of condensation is a function of temperature change. D. Electrochemical sensors normally require relatively much less power. the sensor transmitters are always a few degrees warmer than the environment in order to minimize the possibility of condensation. A properly designed sampling system may make difficult or otherwise impossible applications possible to handle.Hazardous Gas Monitors can cause moisture condensation. Areas with poor air circulation can often be the cause of condensation. This is particularly important in a confined space such as a closed container where air circulation is poor. there is no problem in normal industrial background environments. Therefore. but a carefully evaluated and studied application can yield savings in both time and money. as seen on wet windows and car windshields in the morning. therefore. it is easier for condensation to occur. as long as the air circulation is normal. 106 . It is difficult to mention every consideration needed. their transmitters are designed to operate at 14-24 VDC. A typical specification for humidity is 95% noncondensating. even during the hot summer months in coastal areas such as the Gulf of Mexico. the temperature of their transmitters is similar to the surrounding temperature. which generates heat. In applications requiring the sensors to be constantly exposed to gas. Normally. special considerations are required and the sensor specifications and the suppliers of the sensors may need to be consulted. In addition. E.

Electrochemical sensors are therefore a good choice for portable instruments. The cost 107 . The gas concentrations are high and are generally in the range of several percent. Hence. ranges are typically 100% lower flammable limits or a fraction of these ranges. Summary Electrochemical Sensors. Toxic versus Combustible Gas Monitoring Gas monitoring applications are generally classified into toxic or combustible range monitoring. Toxic gas monitors are generally used for human health protection and the ranges of the monitors are 3 to 5 times higher than the permissible exposure limits. responds quickly to gas. For combustible applications. one can decide which sensor best meets one’s requirements. For portable applications. which maximizes the sensor life. however. for combustible gas monitoring. ranges are in ppm concentrations. Electrochemical sensor life expectancy is two years. it can be much shorter. the electrochemical sensor has many advantages: it has very low power consumption. depending on the application. Except for oxygen applications.Chapter 8 Sensor Selection Guide With the specifications of the sensors. for toxic gas applications. a sensor must be able to measure gases at low concentrations while. the sensors are only exposed to gas periodically. the information that follows contains some guidelines that may be helpful in making the proper selection of a sensor. such as 50% LFL. Also. There is no general consensus that establishes which sensor is the best for a given application. a sensor must measure high gas concentrations. For most gases. electrochemical cell sensors are designed to be used as toxic gas monitors. In other words. These sensors are only suitable for low concentration ppm ranges. and is not affected by humidity.

solid-states sensors and infrared sensors. the choice is between infrared sensors and solid-state sensors. For the rest of the gases (for ppm ranges).Hazardous Gas Monitors of replacement sensors is high. especially when the number of sensors is sizable. For toxic gas applications. infrared sensors have the better performance but detection of gases is limited. the sensors are constantly exposed to environmental background gases. simple applications. There are no standardized specifications for a gas monitor. Depending on the gases to be detected. a catalytic sensor is good for normal. solid-state sensors or PIDs will need to be used. The sensors can last for a long time because they are used sporadically in portable applications. it is generally favorable to use solid-state sensors. Catalytic Sensors. it is best to study the sensor specifications and to consult with the supplier. For gases that can poison the catalytic sensors and make them impossible to use. There are approximately 20 gases that can be monitored by electrochemical sensors. In stationary applications. In applications where interference can be a problem. especially when the number of instruments in use is large. The annual budget and labor to keep the instruments functioning need to be considered. The following table entitled “Typical Specifications for Gas Monitoring Instruments” is a summary of several “requests for quotation” from cus108 . which are fully described in Chapters 4. In portable combustible gases in the LEL ranges. Infrared and Solid-State Sensors. solid-state sensors can detect most chemicals in the LEL ranges. For stationary combustible gas applications. Catalytic sensors are relatively inexpensive but one has to make sure they are made by reputable suppliers. 5. and 6 respectively. On the other hand. the choice is among catalytic sensors.

Provides calibration functions. Groups B. mid. Controller Specifications 1. and diagnosis functions. indicating electrical fault of the sensor 5. 4-20 mA analog output signal for each channel. resistive Common relays for each alarm level (3 relays per channel) Options: Individual relays for each alarm level ( 3 relays per channel) “Fault” relays for each channel. 109 . Typical Specifications for Gas Monitoring Instruments Remote Sensor Transmitter Specifications Gas to Be Monitored: Methyl Bromide. Sensor: Solid-state sensor Temperature: –10o C to 45o C. accepts and processes 4-20 mA transmitter output signal. 3. 2. Power: 14 VDC to 24 VDC Output: 4–20 mA linear output. Three-level alarm set points (low. D areas. Humidity: 95% RH. Provide 24 VDC.Chapter 8 Sensor Selection Guide tomers and is presented here as a reference. C. microprocessor-based. 500 mA for each sensor module. 5 amp. Independent digital display of reading for each channel. Div. three alarm settings. Provides functional adjustments without the need to open the transmitter’s cover. 0–500 ppm. 7. high) with LED indicator for each alarm. and provides protection for outdoor applications. Wall-mounted weatherproof NEMA 4X enclosure. 220 VAC max. Four-channel control unit. noncondensing. 4. Accuracy: 5% Response Time: 50 seconds to 90% full scale Background: Normal environmental conditions Transmitter shall be certified for use in Class 1. Relays: SPDT. 6. 1.

it is good general practice to check the sensor more closely during the first 30 days after installation. a maintenance schedule. However. interference from other gases. The intervals between calibration can be different from sensor to sensor. During this period. Generally. Any possible problems can be identified and corrected during this time. Experience indicates that a sensor surviving 30 days after the initial installation will have a good chance of performing its function for the duration expected. If the sensor functions properly for 30 continuous days. During the first 30 days. the sensor should be checked weekly. Also. this provides a good degree of confidence about the installation. Most problems—such as an inappropriate sensor location. 161 .Chapter 11 Gas Sensor Calibration Chapter 11 Gas Sensor Calibration G as sensors need to be calibrated and periodically checked to ensure sensor accuracy and system integrity. factors that were not accounted for in the design of the system might surface and can affect the sensor’s performance. Afterward. It is important to install stationary sensors in locations where the calibration can be performed easily. it is possible to observe how well the sensor is adapting to its new environment. the manufacturer of the sensor will recommend a time interval between calibration. or the loss of sensitivity—will surface during this time.

Calibration here is simply a safety check. should be established. Normally. As a result. Therefore. this monthly check will also afford you the opportunity to maintain the system’s accuracy. Calibration of the gas sensor involves two steps. The calibration will be performed in the field where sensors are installed so it can occur in any type environment. For area air quality and safety gas monitors. a good reference point 162 . it is much more realistic and practical to zero the sensor using the air surrounding the sensor when the area is considered to be clean. and easily executed by regular personnel. The procedure should be consistent and traceable. First the “zero” must be set and then the “span” must be calibrated. Therefore. use pure nitrogen or pure synthetic air to establish the zero point. the requirements need to be simple. Also. and economical. a monthly calibration is adequate to ensure the effectiveness and sensibility of each sensor. this is not correct.Hazardous Gas Monitors including calibration intervals. unlike laboratory analyzers that require a high degree of accuracy. ambient air normally contains a small percentage of water vapor. The method and procedure for calibrating the sensors should be established immediately. Many analytical procedures. Unfortunately. including some specific analyzer procedures such as EPA methods. This reference point can be difficult to establish. Step One: Setting the “Zero” Reading There is no established standard that defines zero air. repeatable. it is popularly believed that using bottled nitrogen or synthetic air is a good method to zero a sensor. Normal air contains traces of different gases besides nitrogen and oxygen. straightforward. The reason for this is that bottled nitrogen and pure synthetic air are readily available. The calibration procedure should be simple.

The lack of water vapor can cause the zero point setting to read lower than in ambient air making the sensor zero appear to drift. B. This is most noticeable in solid-state sensors and PIDs. most shop air contains small concentrations of hydrocarbons. After this conditioning. shop air is available throughout the plant. Also. making it very accessible and convenient. in many facilities. However. carbon monoxide. . This will give a more realistic representation of the zero point because it will be representative of the local ambient air condition. the air is typically very low in humidity. Also. However. Calibration Methods. Taking all factors such as the type of sensor and the conditions of the application into consideration. such as in an office area. It is therefore imperative to make sure that the 163 H2O O2 CO2 & N2 others Ambient air is the best zero air. A solution to this is that the air can be filtered through activated charcoal to remove most of the unwanted gases and water vapor can be added into the air using a humidifier in the sampling system. the following are some proposed methods of calibration: A.Chapter 11 Gas Sensor Calibration can be in the area where air is always considered clean. based on the operator’s judgment that no abnormal condition exists and the instrument is indicating a close to zero reading. use a plastic bag to get a sample of what is considered to be “clean air” in the facility and expose it to the sensor for a few minutes. and possibly other interference gases. it is important to note that carbon monoxide is not removed by charcoal filters. the procedure to zero the sensor can be skipped. and. It is also a very effective way to differentiate a real alarm from a false alarm. Compressed air has the advantage that it is easy to regulate and can be carried around in a bottle. In applications where the ambient air is normally clean. carbon dioxide. the air can be used to calibrate most types of sensors. When in doubt. This is a very quick and easy procedure.

it cannot be used with solid-state sensors or PID sensors because these sensors require some water vapor in the sample stream. In principle. it usually requires that the operators be more skilled than would usually be required. a mixture of the target gas balanced in the background environmental air is the best calibration gas. Premixed Calibration Gas 164 . thus providing an easily obtainable zero baseline. which is described thoroughly in Chapter 10. a soda ash filter should be used to remove carbon dioxide. 1 Nafion Dryer Tube or Wetting Material To Sensor Adding Moisture to Calibration Gases Step Two: Span Calibration The span calibration can be quite easy or it can be very complicated and expensive. Calibration Gas Flow Meter Regulator Fig. most calibration gases are purchased from commercial suppliers. This is also a very good way to zero carbon dioxide sensors since placing a soda ash filter in-line with the sampling system will remove all carbon dioxide. depending on the gas type and concentration range. However. “Sampling Systems and Designs. A simple solution to this problem is to add a wet tissue paper in the sample line. A. This acts as a humidifier in the sample stream and provides enough water vapor for the sensor to read properly.Hazardous Gas Monitors CO concentration in the shop air is the same as in the ambient air. Another option is to use a Nafion tube. Furthermore. to achieve the best accuracy. Although synthetic air is usually very pure. although this can be done. The following section describes a few methods of span calibration.” Figure 1 illustrates this concept. In practice.

This assembly consists of a pressure regulator.Chapter 11 Gas Sensor Calibration This is the preferred and most popular way to calibrate gas sensors. To get this highly pressurized gas out of the bottle in order to calibrate the sensor. lightweight bottles. The low-pressure bottles are thin-walled. Some mixtures can only be stored in bottles that are specially treated or conditioned. lightweight bottles that are usually nonreturnable and disposable. Flow rates between 600-1000 cc/ min are most common. such as nitrogen. these bottles are normally made of thick-walled aluminum which has a service pressure of 2000 psi. a pressure gauge. but some gases can only be mixed in inert gas backgrounds. In operation. 165 . which provides a constant air flow through the orifice. The orifice flow restrictor is a fitting with a hairline hole that allows a constant air flow at a given pressure difference. Each type of mixture will have Low-Pressure Assembly High-Pressure Assembly a different amount of time before it exFig. Many gases can be premixed with air and stored under pressure. a regulator assembly is needed. Figure 2 illustrates typical models of high. The bottles are available in many sizes but most field calibrators employ smaller. High-pressure bottles are designed to bottle pure hazardous chemicals. the high pressure from the bottle is reduced to a lower pressure of only a few psi.and low-pressure bottle assembly. 2 Calibration Gas Bottles pires or before it can no longer be used. For calibration gases. Models can be fitted with an adjustable pressure regulator so that the flow rate can be adjusted accordingly. Premixed gas mixtures are compressed and stored under pressure in a gas bottle. and an orifice flow restrictor. These small portable bottles come in two different categories: a low-pressure and a high-pressure version.

7) = 35.Hazardous Gas Monitors Detailed information about storage and shelf life can be obtained from the manufacturer.918 cc. a single cylinder can be used to calibrate approximately 30 times. can only be mixed with air and stored under low pressure. If the flow rate of the calibration gas is 1000 cc per minute and it takes approximately one minute per sensor to calibrate. let’s say a given lecture bottle has a 440 cc volume (V). Generally. (P/Pa) where Vmix V P Pa = = = = the volume of the gas mixture the volume of the cylinder the pressure in the cylinder the atmospheric pressure For example. With certain sensors. During calibration. Moisture can be added by following the same procedure described in Step 1 for zeroing the sensor. such as methane. 166 . Assume the bottle has a 1200 psi pressure. some sensors may need moisture to get a proper reading. take the total pressure (P) divided by the atmospheric pressure (Pa) and multiply this ratio by the volume of the cylinder: Vmix = V . To estimate the volume of a pressurized gas in a cylinder. Low vapor pressure gases. such as solid-state sensors. whether the mixture of the gas is in the air or in the nitrogen background will dramatically affect the sensor reading. high vapor pressure gases with low reactivity. carbon monoxide and carbon dioxide. Most highly reactive chemicals are mixed with a nitrogen background. such as liquid hydrocarbon solvents. can be mixed with air and stored under high pressure. The estimated volume of the premixed gas at atmospheric pressure is: (440 cc) x (1200/14.

Chapter 11 Gas Sensor Calibration B. For example. 167 Examples of Permeation Tubes . A calibrator with constant temperature and flow regulation is needed. Permeation devices find most of their use in laboratories and in applications using analytical analyzers. Therefore. it is more difficult to make an accurate mixture and to keep it under high pressure. the concentrations needed to calibrate the sensor are typically too high for the permeation device. for a sensor calibrated to 100% LEL hexane. The rate in which the gas molecules permeate depends on the permeability of the material and temperature. Also. For gas monitoring applications. The gas molecules are either permeated through the permeable container wall or through the end cap. However. At a known rate of permeation at a given temperature. they have been found to be of limited use. high vapor pressure gases permeate too quickly while very low vapor pressure chemicals have a permeation rate that is too low to be of any use. This is because hexane is a liquid at room temperature and it has a low vapor pressure. the rate of permeation for a given gas of interest can be too high or too low for a given application. C. a constant flow rate of air mixed with the permeated chemicals forms a constant stream of calibration gas. Cross Calibration Cross calibration takes advantage of the fact that every sensor is subject to interference by other gases. Therefore. it is usually much easier to use 50% LEL methane gas to calibrate the sensor instead of using an actual hexane mixture. The rate of permeation is constant over long periods of time. Permeation Devices A permeation device is a sealed container that contains chemicals in liquid and vapor phase equilibrium. For example. the permeation tube continuously emits chemicals at a constant rate thus creating a storage and safety problem.

if the instrument is calibrated to methane but is used to measure pentane. Therefore.5. For instance. use 50% LEL methane calibration gas and calibrate with this as 100% LEL pentane. pentane has an output of only half that of methane gas when the sensor is calibrated to methane. The first method is to calibrate the instrument to methane while other gas readings are obtained by multiplying the methane reading by response factors that are included in the manual. The advantage of cross calibration is that it allows the sensor to be calibrated with a gas and range that is easier to obtain and handle. methane has a very high vapor pressure and is very stable. any gas within the same wavelength of absorption can be used for cross calibration.Hazardous Gas Monitors On the other hand. it can be mixed with air and still be kept under high pressure. This is commonly done with catalytic sensors. Therefore. Catalytic sensors have a linear output and therefore the use of this response factor is applicable to the full-scale range.5 to obtain the pentane reading. Also. but double the value of the reading of the calibration. it is common practice for manufacturers of combustible gas instruments to recommend the use of methane as a substitute to calibrate for other gases. After the calibration. The second method is to still use methane as the calibration gas. Many low-range toxic gas sensors can be calibrated using cross gas calibration. it has a response factor of 0. For example. So. 168 . It can be used for many more calibrations than a hexane mixture in the same size bottle and it has a long shelf life. There are two ways to accomplished this task. A 50% LEL methane mixture is also readily available. the reading is multiplied by 0. Furthermore. the instrument directly indicates the pentane gas concentration although it was calibrated using methane gas. with infrared instruments.

Gas Mixing Not all calibration gases are available. To make a 20% LEL mixture having a volume of 2000 cc. One is that the response factors for each sensor can be different as it is generally impossible to make most sensors exactly alike. in catalytic sensors. the following formula can be used: Vb = and Va = V – Vb where Cb = concentration in the bottle. V. it is very possible that they would not be available in the right concentration or in the proper background mixture. 50% in this case C = new concentration. Check with the instrument manufacturer for more detailed information. V C . the response factor will not be applicable. there are some problems with using cross calibration. For example. D. many mixtures are available for some process uses which can be diluted to use in calibration of gas monitors in lower concentration ranges.Chapter 11 Gas Sensor Calibration However. the heater voltage has to be as specified in the manual. 20% in this case V = total final volume.000 ppm. otherwise.5% or 25. 2000 cc in this case Vb = volume of mixture Va = volume of air or other dilutant 169 C . The response characteristics will vary with different heater voltage settings. For example. Cb Va = C – Cb . Mixtures of stable noncombustible and nontoxic gases with various concentrations are available from many supply sources. it is a good practice to periodically check the calibration of the sensor with the actual target gas. Therefore. 50% LEL methane has a concentration of 2. Even if they are available. However.

For very small volume measurements. Hence. and 50 cc 170 . otherwise. Some Calibration Tools To perform the above procedure. there are micro syringes that are readily available in chemical supply catalogues. It provides an easy and convenient means to make a mixture on a regular basis. the following tools are needed: 1. A disposable medical syringe with a large gage needle is most practical but there are few syringes with more than one hundred cubic centimeter volume. 2000 = 8 cc therefore Va = 2000 – 8 = 1992 cc By mixing 8 cc of calibration gas into 1992 cc of air. Vb = 100/25000 . However. it is easy to make a syringe using any standard size pipe having about a 2-inch diameter. food would be contaminated with odor. Syringe and Needle: This is the most inexpensive way to accurately measure the amount of gas. Calibration Bag: Most of the materials used in food packaging or storage are quite inert. 2. Therefore. large volume measurements can be troublesome. 2000 = 800 cc Va = 2000 – 800 = 1200 cc The final mixture would be made by taking 800 cc of the calibration gas and mixing it with 1200 cc of air to make the mixture equal to 20% LEL. Another example is to dilute this 25000 ppm of methane calibration gas to make a 100 ppm of mixture. A 2”-Diameter. 10 cc.Hazardous Gas Monitors Vb = 20/50 . 2000 cubic centimeters of 100 ppm gas mixture is obtained. 1000 cc Syringe Standard Medical Syringes: 1 cc.

Chapter 11 Gas Sensor Calibration food storage bags can be used to hold most chemicals as long as they are used for relatively short durations. This will result in a 2000 psi mixture of 20%LEL methane. For example. take an 800 psi mixture of 50%LEL methane with a 1200 psi mixture of air. It is made from polyvinyl fluoride and has low absorption of gas molecules. Pressure Formula Earlier. However. This is an important point to keep in mind since gas molecules will eventually diffuse through the many thin layers of a plastic bag. we described preparing a mixture based on a volume relationship. There are also many commercially available sampling bags on the market. potato chips can stay fresh in their original bag for long periods of time because the bag material is less permeable by gas molecules than normal food storage bags. 106 ppm where Vc is target gas volume and Vd is the 171 A 5-liter Sampling Bag 1000 cc Calibration Cans Mixing Calibration Gas . This is demonstrated by the fact that when the potato chips are transferred into a tightly sealed food container bag. Following are some examples of how gas mixtures can be made: For ppm gas mixtures: Cppm = Vc /(Vc + Vd) . Sampling bags normally come with a valve and a septum that is used as an injection port. As an illustration. this type of bag is still permeable. Preparing gas mixtures can be a very difficult task. the same volume formula can be used as a pressure formula. so a heavy gauge material will be needed if permeability is a major concern. Based on the ideal gas law. One common example is a Tedlar bag. they will lose their crispness in a very short time. It is best to consult with the instrument manufacturer regarding the best method of calibration and availability of gas mixtures.

This temperature and pressure is also called the standard condition. 109 . V .2 microliters 172 . M/(24. D) V = C ppm a where all units are in milliliters. At standard conditions. To make a calibration mixture for liquid chemicals. 2000 . What is the amount of benzene needed to make a 1000 ppm mixture in a 2000 cc bottle? V = 1000 .88) which yields V = 7. what is the concentration in parts per million when 1 cc of CO is added to a 1000 cc container? C = 1/1000 .5 .0072 cc = 7. 78. Calibrating Liquid Chemical Mixtures. Since it is easier to measure the liquid using a micro syringe. For example. C% For % range gas mixtures: = Vc /(Vc + Vd) . M) ppm a where V = volume of liquid. it is useful to know that one gallon is equal to 3785 cc. 102 % The Vc term in the denominator can be insignificant in low ppm mixtures. and M = the molecular weight of the liquid.5 . which is the same as the specific gravity. cubic centimeters. 106 = 1000 ppm ppm Many containers are sized by gallons. (V x D)/(V . and grams. The ideal gas law states that one gram mole of molecules will occupy 24. Therefore.500 cc of volume at 25 degree centigrade and at 760 mm of mercury or sea level atmospheric pressure.Hazardous Gas Monitors dilutant volume. D = density of the liquid.1/(24. 109 . For example. the equation is: C = 24.1 g and D = 0. Va = the volume of the dilutant air. benzene has M = 78.5 . 10-3 = 0.88 g/cc. a known volume of liquid is vaporized in a known volume of dilutant air. 109 . the equation then becomes . 0.2 .

again assuming standard conditions. and medical toxicology work. However.Chapter 11 Gas Sensor Calibration Ventilation Hood for Calibration Procedures In air pollution. data can be normalized at a later date if necessary. 173 . industrial hygiene. accuracy is not extremely important because these are not analytical devices or systems. Cppm = C . If procedures are standardized.5/M where C = mg/m3 M = molecular weight In conclusion. for the calibration of gas monitors. 24. it is most important to keep the calibration methods standardized and easily traceable. The following equation expresses this relation. the commonly used unit of concentration is milligram per cubic meter.

14 9.3Butane Butanol.7 C IP (eV) C2H4O C2H4O2 C4H6O3 C3H6O C2H3N C2H2 C3H4O C3H4O2 C3H3N C3H6O C3H5Cl H3N C5H12O C7H7N C7H8O C7H6O C6H6 C7H5N C7H7Cl C6H5Br CHBr3 C3H7Br C4H6 C4H6O2 C4H10 C4H10O C4H8 C6H14O2 1.2 5.55 + 0.7 + 0.62 (Courtesy of RAE Systems.6 C 11.6 + 2. relative humidity.16 10.98 10.4 100 2 1. 191 .40 10.6 2. Database 19A.60 10. 1Butoxyethanol.9 10.18 9.) Notes: 1.8 C 10.25 9. The correction factors in this table were measured in dry air.49 9.10 10.50 + 0.0 1.6 1.2 1. and NIST Standard Ref.3 + 9.72 8.5 + 150 + 1.2 1.7 5.8 1 0. the instrument should be calibrated regularly under the operational conditions in which the instrument is used. all others are preliminary and subject to change.7 + 5 0.5 0.1. 3. 73rd Edition.48 10. IP (eV) data was taken from the CRC Handbook of Chemistry and Physics. 2.21 9. 1Butene.1 + 10.4 + + + 8.99 9. Actual readings may vary with age and cleanliness of the lamp.9 + 12 + NR 4.7 0.67 9.23 10. 2- Formula 9. components in the sample. For accurate work.7 + + + + + + + + 6.19 11.66 10.1Butadiene Butadiene diepoxide.5 + + 2.4 2.2 + 0.5 + 1.91 9.5 + 0.1 + + 1.07 ~10 10.5 0. and other factors.0 + + 3.8 70 + 4.53 9.5 + 1. The values indicated by a plus (+) sign in the “C” column are confirmed values.9 + 1.6 + 0.00 7.58 <10 NR 42 + 3.6 + 25 NR 0. Inc.4 + NR NR 1.2 1.0 1.1 1.5 + 0.7 C IP (eV) PID Correction Factors for Various Gases and Lamps with Instrument Calibrated to Isobutylene Compound Name Acetaldehyde Acetic Acid Acetic Anhydride Acetone Acetonitrile Acetylene Acrolein Acrylic Acid Acrylonitrile Allyl alcohol Allyl chloride Ammonia Amyl alcohol Aniline Anisole Benzaldehyde Benzene Benzonitrile Benzyl chloride Bromobenzene Bromoform Bromopropane.71 12.6 C 11.5 + + 22 + 2.Appendix I PID Correction Factors Appendix I Compound Name Formula 9.8 C 10.7 0.6 2 0.

44 + 0.47 + 0.6 + 1.5 NR NR + 1.40 + 0.58 + 0.7 1.0 NR + 1.1-difluoroethane.95 8.4 + 0.52 NR + 2. o Formula 9.1 1.2.73 11. nButyl acrylate. oChlorotoluene.51 9.5 + + 11.4 + 1.C3H7ClO 192 .5 1.62 10.34 9.8 + 1.7 + + 3.2 10.6 + 8.6 0.7 C IP (eV) C6H12O2 C7H12O2 C4H11N C4H10S CS2 CCl4 Cl2 C4H5Cl C6H5Cl C2H3ClF2 CHClF2 C2H5Cl C2H5ClO 3 NR + NR 0.Hazardous Gas Monitors Compound Name Butyl acetate.07 11. 2Chlorobenzene Chloro-1.2 + NR + 0.1 + NR NR 1.48 10 Chloroethyl methyl ether.37 9.47 11.86 9.84 12.65 CHCl3 C7H7Cl C7H7Cl C4H6O C9H12 CNBr CNCl C6H12 C6H12O C6H10O C6H10 C6H13N C5H10 C10H22 C6H12O2 C2H4Br2 C6H4Cl2 NR NR + 3 0. 1.6 1.37 8.06 12.38 + 0.6 C 11.(R-142B) Chlorodifluoromethane Chloroethane Chloroethanol Chloroform Chlorotoluene.0 + + 0.73 8.0 + 0.3-butadiene.2Dichlorobenzene.3 1. nButylamine Butyl mercaptan Carbon disulfide Carbon tetrachloride Chlorine Chloro-1.75 9.6 + 7 0.8 C 10. 1.97 10.39 + NR NR NR + NR NR 1.4 + 0.0 12.9 + 0.54 + 0.6 4. pCrotonaldehyde Cumene Cyanogen bromide Cyanogen chloride Cyclohexane Cyclohexanol Cyclohexanone Cyclohexene Cyclohexylamine Cyclopentane Decane Diacetone alcohol Dibromoethane.2 0.08 0.1 + 9.6 + 10.69 9.5 1.83 8.14 8.5 0.7 + 1.4 NR NR + + 0.0 0.71 9.14 10.7 + 0.

2Ethyl acetate Formula 9.6 10.87 + 0. t-1.8 + 1.7 + 1 1.6 + + 193 .7 + + + 10.6 C 11.3 4 0.8 + 8. 1.79 9.5 + NR + 0.19 10.75 11.8 + 1.51 9.Appendix I PID Correction Factors Compound Name Dichlorodifluoromethane Dichloroethane.3 2.52 10.7 0.5 + ~4 + 10 3. 226 m. 3Diethylmaleate Dimethylacetamide.81 8.w.96 10.NDimethylamine Dimethyl disulfide Dimethylformamide. 2. 1. 1.5 4.2.NDimethylhydrazine.2Dichloroethene.1.9 NR + 1.01 C2H5ClO ~200 + 8.28 + 8.13 7. N.8 0.w. 1.3 + + NR NR + NR 0.7 C IP (eV) CCl2F2 C2H4Cl2 C2H4Cl2 C2H2Cl2 C2H2Cl2 C2H2Cl2 C2H3Cl2F C3H6Cl2 C3H4Cl2 C2HCl2F3 m.1.4 15 8 ~3 3 + + + NR 12 + + 0.2 + 0.9 + 0.8 0. 1.2Dichloro-1-fluoroethane.2 1.1 1.06 11.1Dichloroethene.2Dichloroethene.1Dichloroethane.(R-123) Diesel Fuel #1 Diesel Fuel #2 Diethylamine Diethylaminopropylamine.5 + 0.3 0.66 9.8 C 10.23 7. c-1.4 + 0.4Epichlorohydrin Ethane Ethanol Ethanolamine (Not Recommended) Ethene Ethoxyethanol.(R-141B) Dichloropropane.0 0. 2. 216 C4H11N C7H18N2 C8H12O4 C4H9NO C2H7N C2H6S2 C3H7NO C2H8N2 C2H6O4S C4H8O2 C2H6 C2H6O C2H7NO C2H4 C4H10O2 C4H8O2 ~23 0.87 <10 11.1 + 0.9 0. 1. N.8 + + 9.2 Dichloro-1-propene.1-trifluoroethane.2 11.20 + 0. 1.5 + 0.3Dichloro-1.6 + NR + NR + 11.4 9.47 8.65 + 10.1Dimethyl sulfate Dioxane.04 9.01 ~20 + 2.

44 2.5 + + 9.51 10.1 19 + + 4.Hazardous Gas Monitors Compound Name Ethyl acrylate Ethylamine Ethylbenzene Ethylene glycol Ethylene oxide Ethyl ether Ethyl formate Ethyl hexyl acrylate.1.1 NR NR 1.6 C 11.8 C 10.HMDS C6H19NSi2 Hexane. 92 octane Glutaraldehyde Halothane Formula 9.3. 1.9 + 0.0 + + 0.29 8.1 + 100 + + 3.6 + NR NR + + 2.5 6 3 + + + 1.6 10.1 1.5 + 0.1-trifluoroethane.5 1.52 + 0.5 + + + + + + 8.8 0. R-123) HCFC-141B (see 1.77 10.40 10. 72 m.2 + 0.1 + 1.3 1.3 + + 0.92 ~8.43 10.5 0.1-Dichloro-1-fluoroethane) HCFC-142B (see 1-Chloro-1.3.1.57 9.6 + + ~10 9.5 0.1 0.2 + 300 0. 2Ethyl (S)-(-)-lactate Ethyl mercaptan Ethyl sulfide Formaldehyde Furfural Gasoline #1 Gasoline #2.5 + 16 + 19 + 1.43 10.6 0.6 + + 11.2-Dichloro-1.8 NR NR NR 0.3) 8.1-difluoroethane) Heptane.87 9.16 10. n Hexene.4 + 0.8 + 194 .9 0.8 + 0.86 8. 1Hydrazine Hydrogen Hydrogen peroxide Hydrogen sulfide Iodine Isobutane Isobutanol C6H14 C6H12 H4N2 H2 H2O2 H2S I2 C4H10 C4H10O + 3.1 + + 3. nC7H16 2.6 0.21 0.57 10.54 10.6 + 0.9 + + 1.0 + (<10.2 0.13 Hexamethyldisilazane.61 HCFC-123 (see 2.w.8 + 2.45 9.6 0.3 + 9.1 15.w.2 1.3. 93 C5H8O2 C2HBrClF3 1.0 13 1.7 C IP (eV) C5H8O2 C2H7N C8H10 C2H6O2 C2H4O C4H10O C3H6O2 C11H20O2 C5H10O3 C2H6S C4H10S CH2O C5H4O2 m.5 0.02 0.1.

86 + 0.7 C IP (eV) C4H8 C7H12O2 C3H2ClF5O C8H18 m.9 + + 1.5 1. 191 C9H14O C5H8 C3H8O C5H10O2 C6H14O m.1 NR + 0.64 11.2 + 1.6 1.3 + + NR NR + + 1. 148 m.97 10.12 9.4 0.5 + 0.69 + 0.00 + 1. 167 m.9 + + 0.8 2.4 0.0 110 + 1.2 + + + + + + + + + 8.7 9.w.4 + + 1.07 8.3 + 500 + 6.41 12.7 + 9.86 1.00 + 1.1 <10 10.4 3 0.6 + 0.3 0.9 + NR 1.7 + 0.4 + NR + 3.w.1 1.distillate .6 C 11.32 9.60 + 9.w. 115 m.20 9.see Jet Fuels) + 2.w.89 + 1.7 + 0.3 NR 2.22 9.7 + 1.9 1. 2Methoxyethoxyethanol.6 + 0.24 11.7 + 1.2 + Methyl cellosolve (see 2-Methoxyethanol) 195 .85 10.2 + + 0.00 + 1.54 9.3 0.85 10.30 0.5 0.27 (9.35 + NR NR 4.4 0.60 + 2. 165 C9H12 CH4 CH4O C3H8O2 C7H16O3 C3H6O2 C4H6O2 CH5N CH3Br C5H12O CH3Cl C7H14 CH2Cl2 C4H8O C2H6N2 C6H12O NR 1.0 + 2.Appendix I PID Correction Factors Compound Name Isobutene Isobutyl acrylate Isoflurane Isooctane Isopar G Solvent Isopar M Solvent Isophorone Isoprene Isopropanol Isopropyl acetate Isopropyl ether Jet fuel JP-4 Jet fuel JP-5 Jet fuel JP-8 Mesitylene Methane Methanol Methoxyethanol. 2Methyl acetate Methyl acrylate Methylamine Methyl bromide Methyl t-butyl ether Methyl chloride Methylcyclohexane Methylene chloride Methyl ethyl ketone Methylhydrazine Methyl isobutyl ketone Formula 9.36 + 0.24 Kerosene (C10-C16 petro.51 7.5 0.8 C 10.w.99 9.8 1 + 0.6 + 0.51 10.9) 8.8 + 0.

3 2.51 9.Hazardous Gas Monitors Compound Name Methyl isocyanate Methyl mercaptan Methyl methacrylate Methyl propyl ketone Methyl-2-pyrrolidinone.35 Peracetic/Acetic acid mix C2H4O3/C2H4O2 0.13 9.6 + 0.4 + 0.1 0.4 0.81 10.6 + 8.40 + 2 13.0 C10H8 NO C6H5NO2 C2H5NO2 NO2 CH3NO2 C3H7NO2 C9H20 C8H18 C5H12 C2H4O3 C2Cl4 C6H12O3 C6H12O3 C6H6O PH3 C6H7N C10H16 80 NR 2. nPentane Peracetic acid Perchloroethene PGME PGMEA Phenol Phosphine in N2 Photocopier Toner Picoline.75 11. aMineral spirits (Stoddard Solvent.8 + 2 0.7 C IP (eV) C2H3NO NR + 4.5 10.8 + + 8.82 + + 0.72 9.88 + 9.5 1.0 + 1.0 0.8 1.2 + 1.67 CH4S C5H8O2 C5H12O C5H9NO C8H8O3 C9H10 1.6 C 11.18 1.9 + + 9.0 + 9.8 0.45 + 0.69 + 0.32 8.8 0.5 + 0.07 196 .31 + + + + 1.17 0.65 + 1.8 C 10. see also Viscor 120B) Mineral Spirits Viscor 120B Calibration Fluid Naphthalene (Mothballs) Nitric oxide Nitrobenzene Nitroethane Nitrogen dioxide Nitromethane Nitropropane.04 8.26 9. 3Pinene.39 + 1.9 + + 0.71 9.7 + 0.7 9. a- Formula 9. NMethyl salicylate Methylstyrene.0 + 2 0.7 2.5 8.5 + 0.3 + 0.4 + 0.3 + + + + 10.57 + 0.6 3 NR 4 2.9 0. 2Nonane Octane.6 1.87 9.6 + 1.02 10.3 2.7 + 5.4 0.44 9.5 + + 1.38 9.2 + + 1.9 1.9 + NR + 0.4 + + NR + 50 + 2.4 1.

Appendix I

PID Correction Factors

Compound Name Pinene, b Piperylene, isomer mix Propane Propanol, nPropene Propionaldehyde Propyl acetate, nPropylene oxide Propyleneimine Pyridine RR7300 (70:30 PGME/PGMEA)

Formula 9.8 C 10.6 C 11.7 C IP (eV) C10H16 0.38 + 0.4 + 0.4 + ~8 C5H8 C3H8 C3H8O C3H6 C3H6O C5H10O2 C3H6O C3H7N C5H5N 1.5 0.76 + 0.7 + NR 6 1.7 + 1.9 3.5 6.5 + 1.3 + 0.78 + 0.7 + + 1.0 + 2 1.0 0.7 + + + 0.6 1.8 1.7 + + 8.6 10.95 10.22 9.73 9.95 10.04 10.22 9.0 9.25

C4H10O2/ 1.4 C6H12O3 C8H8 SO2 NR 0.4

Stoddard Solvent - see Mineral Spirits Styrene Sulfur dioxide 0.45 + 0.40 + NR + NR 0.3 0.7 + NR NR 1.9 0.90 + C7H8 C2H3Cl3 C2H3Cl3 C2HCl3 C2Cl3F3 C6H15N C2H3F3 NR + C9H6N2O2 1.4 + + 1.7 + 0.7 + 8.82 11 11.0 9.47 11.99 7.50 34 12.9 2.0 1 0.9 0.4 NR + + + + + 0.4 NR 1.3 + 0.60 + 0.2 0.2 NR NR 1.0 + + >15.3 9.41 + + + 8.43 12.32 ~11.1 ~11.1 ~11.1 ~9.8

Tetrachloroethane, 1,1,1,2- C2H2Cl4 Tetrachloroethane, 1,1,2,2- C2H2Cl4 Tetraethyllead Tetraethyl orthosilicate Tetrafluoromethane Tetrahydrofuran Therminol Toluene Tolylene-2,4-diisocyanate Trichloroethane, 1,1,1Trichloroethane, 1,1,2Trichloroethene Trichlorotrifluoroethane, 1,1,2- CFC-113 Triethylamine Trifluoroethane, 1,1,2C8H20Pb C8H20O4Si CF4 C4H8O

Tetrafluoroethane, 1,1,1,2- C2H2F4

0.54 + 0.50 + 0.51 + + 1.4 + NR NR + +

0.62 + 0.5 + NR 1.3

197

Hazardous Gas Monitors

Compound Name Trimethylamine Turpentine Undecane Vinyl actetate Vinyl bromide Vinyl chloride in N2 Vinyl-2-pyrrolidinone, 1Xylene, mXylene, oXylene, p-

Formula 9.8 C 10.6 C 11.7 C IP (eV) C3H9N C10H16 C11H24 C4H6O2 C2H3Br C2H3Cl C6H9NO C8H10 C8H10 C8H10 1.0 0.9 0.4 2 1.2 0.4 2.0 + + 0.8 + 0.6 0.9 + + 8.56 8.56 + 8.44 9.56 9.19 9.80 9.99 7.82

Trimethylbenzene, 1,3,5- - (see Mesitylene)

Viscor 120B - see Mineral Spirits - Viscor 120B Calibration Fluid 0.50 + 0.4 + 0.40 + 0.57 + 0.6 + 0.5 + 0.7 0.6

198

Thermocatalitic sensor in dynamic mode
1. General principle Schematic diagram of sensor for methane concentration in dinamic mode is shown on the figure below:
C0

1

2

C

3

4

1. Cover made of strained metal chippings or porous ceramic 2. Calibrated hole between prechamber and combustion chamber 3. Combustion chamber Thermocatalitic element, platinum coil with small temperature inertia Co - concentration of the gas outside the sensor C- concentration of the gas inside the combustion chamber St —overall signal (current or voltage) which is result of heathing of the coil from curent flow and of gas combustion onto the coil.

St Figure 1

When the coil is powered, it will start to heat up, and gas into chamber will start to combust. At the beguinning inflow of the gas through calibrated hole is smaller then the quantity of the combusted gas onto the coil, concentration of gas C will be reduced. When the quantity of combusting gas becomes equal to quantity of inflow gas, concentration stabilize with new value Ci (see diagram 3). It is easy to show theoreticaly, and experiments certify, that gas concentration into chamber reduce with exponential trend. At the moment when concentration almost reach Ci, power is turned off and the chamber starts to fill again, it fills up for about the same time. The power is turned on again and so on alternatively. Transitive process in which we measure the signal in two consecutively points is repeated, and on that base we determine concentration of the target gas, as we will see later. It is validated truth that transitial process is much more reliable and much informational than the stationar.

r ) e-t/T] Where are : r = Ci/Cs factor of concentration reduction. coil starts to heat up rapidly caused from current and also from gas combustion until the signal reach its maximal value Ss (period II). Other part of the signal. flux of outer gas inflowing through the hole is smaller than the quantity of the combusted gas and the concentration decrease ‘till reach equilibrium point when the signal becomes Si. The both of this factors are characteristics specific for each. St= S + Spar . which is of the greatest interest for metrology. parasitic signal. of course. humidity. resistive changes with time. Signal then stays constant on minimal value Si (period 4). it folows: S = k Cs [ r + (1 . etc. The following trend of exponencial decreasing of the concentration in the period III is changing by following formula: C = Cs [ r + ( 1 . It also consists of other relevant factors as is the air pressure. Time t is calculated from the end of the period II (t=0). Because the signal is proportional with concentration S = k x C. after that time. a signal remains null (period I). only a part fo the signal and its origin is from the gas combustion.r ) e —t/T ] This is. In the period III.Ss Si I II III IV Figure 3 One short time period after energizing the coil (t=0) there is no respond from system and that is inertial time of the system. is the result in the first place of resistor heating caused by current flow but its also caused by ambient temperature. and T — is time constant.

Selection of the points t1 and t2 in which we measure the signal is of great importance. classical explosimeters shows accurately only concentration of gas for which they are calibrated and indicate it in percents of lower explosive limit (LEL). It’s stated before that it is beter to have coil with as smaller thermal inertia as it is possibile. Instrument realized on basis with thermocatalitic sensor in dinamic mode The stated principle is able to realize only with use of micro-controller. We will comment only briefly some of them. As a matter of fact. Measuring range of this device is from 0-100% methane. This makes those exposimeters practically useless. The diameter of the calibrated hole and the capacity of combustion of coil. t2 ) = S (t1) . in areas where we don’t know which gas is present. installed in the same measuring chamber another catharometric sensor wich cover range of 5-100% methane. The difference of the signals in those two points L (t1 .Signal total St Ss L = St(t1)-St(t2) Si Spar t=0 t1 t2 Temps (Unités arbitraires) Figure 4 On this curve coordinate beguinning (t=0) is shifted at the end of period II. but when it is achieved by minimizing the vire dimesions and coil itself. level of the Ci (Si) and the time for reaching that value (time constant). which is done in cooperation of French company Oldham and Russian laboratory NPC-ATB. The proper choose of this two parameters enables construction of so called “universal” explosimeter. because during time coil characteristic gets deformed and maximum point is sliding slowly towards right side. it has beside catalitic sensor in dinamic mode. From theory stated above it can be seen that the number of parameters are before the constructor to adapt them in the best way to his specific applications. 2. Point t1 should be chosen far enought from maximal value. which works in range of 0-5% methane. Dinamic mode enables to. determining its gradient. Total signal is measured in two points t1 and t2 on transition curve. with proper chose of parameters t1 and t2. . and measuring of explosivity itself can deflect up to 300% in extreme cases. It won’t be same for stationary devices in mines which are constantly exposed to target gas and devices in industry (stationary or portable) where the presence of target gas is mostly incidently. thermocatalitic surface layer should achieve very intensive combustion and in that way increase sensitivity of sensor itself.S (t2) is proportional with gas concentration. or when there is a mixture of gases. to avoid shifting of that point to left side from the maximum. and it is realized and specific measuring instrument is called DMS-01. are obviously in relation to each other. realize explosimeter wich will equaly acurate measure explosivity of mostly combustile gases. and for extreme cases deflection is below few tenth of percent (referred to curently 300%). Any other explosive gas they only indicate. The distance between points t1 and t2 is from great importance. The diameter of calibrated hole considerably influence on the form of exponential curve.

but only if the concentration is less than DGE. otherwise it turns on.35 sec.0.. is shown on following figure: . If a methane concentration is above level of DGE (5%CH4). sensor for lower concentrations stays turned off. the slope is under lower angle because the wire start to cool more intensive (element is constantly energized) this is previously stated distinction of the catarometric sensors. Time line of one measuring cycle.Design of measuring cell (sensor) is given on following figure: gas sinter 0. micro-controller turns on thermoconductive sensor for high methane concentrations HC with short current impulse which lasts for 0. in case that after initial turning on the DMS-01 has measured concentration below DGE. during that time thermocatalitic sensor is turned off (no methane combustion).5 .7mm HC LC Principle of opertion is as follows: first of all. As the concentration of methane is higher.

Quantity of the gas that combust is in proportion with concentration of the gas that’s inside the chamber. when proper temperature is reached (about 450°C) and combustion of methane starts. . it is installed in a chamber with calibrated hole 0.35 sec 2 — sensor response HC 3 — current impulse for heating the LC sensor.1 — short current impulse for thermoconductive sensor. 4 — sensor response LC in lack of methane 5 — sensor response in presence of methane Briefly. and after some particular time. lasting for 0. The gas pass thru this calibrated hole. Transition process from the moment of turning on ‘till stabilization is used for measuring. lasting for 2. sensor (LC) turns on and when wire reach proper temperature the methane combustion starts. and the second one at 2.5 — 0.3 sec. first point is at 1. the balance renew.5 sec (turns on at t=1s and turns off at t=3. Concentration is equal to difference of these two signals. LC sensor is a tipical thermocatalitic sensor.3 sec.7mm. (after turning on the sensor). Measuring is conducted in two points. because the power supply of the sensor is turned off.5s ).

and which lead to zero drift. which is inevitable. we determine the gas concentration. sensor HC is turned off.5 sec.41V. avoiding in that way any inconvenience which reference element can cause (need for selection — complying of elements.5 sec for heating. with intrinsically safety conditions in compy with limit curves (IEC 79-11) witout any problems. derived with a safety factor of 1.5. at the temperature of 50°C (mixture is in comply with group of gases IIA). I=116 mA.3% and ambient air. Inlet of the target gas inside the sensor is thru sintered mass which eliminate possibility of intruding of coal dust inside the sensor. without reference. Iib=116 mA.. to fill the chamber again. Summary Thermocatalitic sensors in dynamic mode of operation has following advantages compared to “classical” thermocatalitic sensor: 1.3s 1s After impulse of 2. for cooling down). Thanks to exceptional low power consumption enough for accurate sensor operation (low wire diameter). its created the effect of developing a rather low amount of thermal energy.1. a high temperature coefficient of resistive change ( K=3.. Analysis of Ex protection for thermocatalitic sensor in dynamic mode The next results are achieved in establishing a special conditions for Ex protection: Power supply of the sensor via electronic circuitry with intrinsically safety with maximal values of electrical parameters: Um=1. and the whole process is cyclicly repeating.41V. and 5 sec. and which is a far lower from maximal safety temperature tbez=295°C. in presence of mixture of propane 5. Measurements in stated example are achieved with power supply conditions U=1. that means the operational principle of dynamic mode. 3. and rather low thermal inertia (measuring cycle lasts for 7. Total cycle of measurment lasts for 7. Farther work of this device is on the same principle as after turning on (when the concentration falls below DGE. far from the limit curve. and is cyclicly repeating.9 x 10-3). i. - Design of the sensor. etc. different aging of this two elements. Limited heating of the thermoelement to safety limit (≤ 450°C).3s 2.e. which lead to higher permited temperature limit inside the sensor from 1500 to 450°C.) .5 sec. operative with the comparative. have allowed to designers to construct the measuring intrument. and sensor LC turns on). there is a pause of 5 sec. which leads to low operating temperature of the sensor (Tmax=73°C). 2. 4. With only one element.5 sec. untill to moment when sensor of lower concentration exceed the DGE (5% methane) when the sensor of higher concentration HC turns on.

This make them practically useless. Any other explosive gas. thin wire of 10 μm heats and cools down very quickly. thus only one element is heating (consumption is 50% reduced). thus eases in a great way construction of detector itself.2. or when there is a mixture of gases. Dynamic mode allows us to realize explosimeter. because there is no reference element.5sec) and 5 sec is the time for new charging of the chamber (additional consumption reduction). with proper selection of parameters (t1 and t2). Sensor isn’t working all the time (only 2. and for those extreme cases deflection is around few tenth of percents (referred to curently 300%). 4). comparative. General conclusion is. Ex protection of this sensor is Ex ia. And finally. With dynamic mode. 4.e. Particulary. in areas where we don’t know which gas is present. it is referent to itself. changed thermocatalitic sensor in dynamic mode of operation has its distinctive position as well in mining as so in industry. 3. classical explosimeters shows acurate readings only for concentrations of gas for which they are calibrated for and indicate it in percents of lower explosive limit (LEL). 5. realised in Ex d. Proper choose of parameters of thermocatalitic sensor in dynamic mode allows construction of so called “universal” explosimeter. those changes are the same in points t1 and t2. which will equaly acurate measure explosivity of most of common combustive gases. Power consumption of sensor itself is manifold smaller in compare to classical thermocatalitic sensors. (figure No. actually we compare element with itself. Unlike classical thermocatalitic sensors which has to be installed in flameproof housing. On that way problem of zero drift is solved which is one of the biggest advantages of this sensor. they only indicate. and readings itself of the explosivity could deflect up to 300% in extreme cases. i. if its characteristics change over time. . that the despite of use of IR sensors.

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