ANALYTICAL INSTRUMENTATION ANALYZERS

SILICA ANALYZER:
In thermal power plants, silica content is measured in steam before turbine.silica analyzers are also used for anion exchanger effluent monitoring of mixed-bed exchangers. A silica analyzer manufactured by Electronic Instruments Ltd(EIL), U.K. for continuous automatic stream monitoring works on the calorimetric analysis principle which is based upon the well known molybdenum blue method. Ammonium molybdate solution (pH7), sulphuricacid and a reducing solution are added to a metered volume of sample via separate measuring cylinders (to eliminate the precipitation of molybdic acid).

The flow diagram of the analyzer. The inlet is at the top to prevent contamination by any solution from the previous analysis, and the cuvette is drained completely after every analysis cycle to prevent the accumulation of gas or air bubbles in the measuring cuvette. The analysing cycle takes twelve minutes and consists of two overlapping sequences. The first measures a chemical blank. The second is the actual quantitative determination. An associated sequence timer controls the programme of operations.In the first sequence, ammonium molybdate solution, sulphuric acid and reduction solution are simultaneously added to the mixing vessel. This solution is diluted with sample to a suitable volume and is then emptied into the measuring cuvette where it is measured and then drained away. In the second sequence, the reagents are added in the normal order; sample first then ammonium molybdate and sulphuric acid. The reduction solution is added five minutes later. All materials coming in contact with analysis liquor are either made of plastic or of metal components coated with plastics. The reason for the use of blank on each cycle is to give the analyzer long term stability by compensating for the effects of variables such as coloration of the sample or reagents, temperature, or ageing of the lamp of photo cells. The silicon photo-voltiac cells are conventionally illuminated by a common light source. They are connected in parallel opposition and the differential signal is fed into a very low input impedance current amplifier. For the measurement of the blank solution, the Auto-Compensation Unit (ACU) driven by the current amplifier is connected to its internal motor potentiometer which corrects the zero of the current amplifier. For the measurement of silica concentration, this correction remains fixed and the output from the ACU is connected to the read-out unit. The ACU now controls a motor driven potentiometer in the read-out unit, producing a current output to feed a meter or recorder. A scale length control adjusts the gain of the amplifier. Temperature compensation of the amplifier output, for changes in sample temperature, is provided by a thermistor located in the analyzer constant head unit. The analyzer is normally supplied in a cubicle, complete with analyzer, measuring electronics, and manual facilities for testing and calibration. Reagents are contained in the rear of the cabinet and these require regular replenishment. To assist in providing reliable and repeatable measurements, the complete cabinet is temperature controlled by the use of the thermostas with electrical heaters.

SODIUM ANALYZER:
Sodium analyzers find applications in thermal power plants for determining sodium ion concentration in boiler waters, monitoring carryover detection of condenser leaks and the exhaustion of water treatment plant cation exchange units. The sodium analyzer manufactured by Electronic Instruments Ltd(EIL), U.K. is based upon the use of a specific ion electrode. In fact, ion selective electrode(ISE) is today considered to be one of the most powerful tools for specific analysis, i.e. to determine the specific constituents like cyanide fluoride, NH3 etc. in sample; and is thus widely used for industrial water pollution monitoring. ISE is an electrochemical sensor that develops an electric potential which can be related to the concentration of a specific ion in solution. The potential developed is actually proportional to the logarithmic of the ion activity, which can differ greatly from ionic concentration in non-dilute solutions. Where activity is a measure of the number of free (dissociated) ions in solution, concentration includes both free and bound (undissociated) ions. As the interest in this case is for concentration and not activity, the bound ions must first be liberated so that they can contribute to the measurement. As certain ions in the sample interfere with the specific measurement either by forming bonds with the ions to be measured or by being measured themselves it is essential that the sample be prepared properly before making any measurement. Sample is preferred by adding a reagent which forms bonds with the interfering ions, thereby either freeing the ions of interest, or preventing the interfering ions from entering into the measurement. If the concentration of interfering ions(like H and OH ions)be too high, then the adjuster solution will not be able to provide this over-riding ionic strength, and for such case sample pH must be adjusted to within desired range.

The pH value of the sample is maintained in the flow cell by adding ammonia gas to the sample. A calomel reference electrode is used to complete the electrode pair across which a potential is developed dependent on the sodium ion activity in the sample. The potential is proportional to the logarithm of the sodium ion concentration, thus enabling low concentrations to be measured accurately and also provide high range capacity. The sequence of operation is as follows. Sample water flows to a constant head tank to ensure a fresh sample and it is pumped anaerobically. At a constant rate, into the flow cell, where it is equilibrated with ammonia gas. The ammonia gas is derived by pumping air through a 25% ammonia solution and passing the ammonia saturated air to the flow cell. The sample then flows past the measuring electrodes to a drain outlet. The analyzer also includes a facility for automatic standardization. The standardization sequences commences by activating a valve to stop the sample flow and to allow the standard sodium ion solution to be pumped into the flow cell. When the electrodes have stabilized in the new solution the amplifier output is compared with a pre-set standard value in the auto compensation unit, and any error is used to drive a servo potentiometer circuit, to adjust the output to the correct value.

Cleaning of electrode at specified interval is essential for electrode longevity and accuracy. Some manufactures have automated the procedure of cleaning using solid state timers and achieving electrode cleaning by mechanical (brush), spray nozzle, or acoustical means. In mechanical system the brush strokes the probe 2-4 times in minute; in chemical method, clean fluid is sprayed on membrane and in acoustical method, ultrasonic waves vibrate deposits off the spray ISE based monitors can be used for measuring the following effluent parameters Ammonia Chloride Copper Cyanide Fluoride Nitrate Nitrite Sulphide Water hardness etc.

PH meter
A pH meter is an electronic instrument measuring the pH (acidity or alkalinity) of a liquid . A typical pH meter consists of a special measuring probe (a glass electrode) connected to an electronic meter that measures and displays the pH reading. The pH probe measures pH as the activity of hydrogen ions surrounding a thin-walled glass bulb at its tip. The probe produces a small voltage (about 0.06 volt per pH unit) that is measured and displayed as pH units by the meter.

Calibration and use:For very precise work the pH meter should be calibrated before each measurement. For normal use calibration should be performed at the beginning of each day. The reason for this is that the glass electrode does not give a reproducible e.m.f. over longer periods of time. Calibration should be performed with at least two standard buffer solutions that span the range of pH values to be measured. For general purposes buffers at pH 4 and pH 10 are acceptable. The calibration process correlates the voltage produced by the probe with the pH scale. After each single measurement, the probe is rinsed with distilled water to remove any traces of the solution being measured, blotted with a clean tissue to absorb any remaining water which could dilute the sample and thus alter the reading, and then quickly immersed in another solution.

Types of pH meters
1. Null Detection Type PH meter 2. Chopper Amplifier Type PH meter.

Null-Detector Type pH Meter:

Chopper Amplifier Type pH Meter:

Electrodes for pH measurement:

There are different types of electrodes for the measurement of pH. Such as 1. Hydrogen electrode 2. Glass electrode 3. Calomel electrode or Reference electrode 4. Silver/Silver chloride Reference electrode

Hydrogen electrode:

Glass electrode:

Calomel Electrode or Reference Electrode:

Silver/Silver Chloride Electrode:

CONDUCTIVITY METER
An electrical conductivity meter (EC meter) measures the electrical conductivity in a solution. Commonly used in hydroponics, aquaculture and freshwater systems to monitor the amount of nutrients, salts or impurities in the water.

An electrical conductivity meter

Principle of operation:
The common laboratory conductivity meters employ a potentiometric method and four electrodes. Often, the electrodes are cylindrical and arranged concentrically. The electrodes are usually made of platinum metal. An alternating current is applied to the outer pair of the electrodes. The potential between the inner pair is measured. Conductivity could in principle be determined using the distance between the electrodes and their surface area using the Ohm's law but generally, for accuracy, a calibration is employed using electrolytes of well-known conductivity. Industrial conductivity probes often employ an inductive method, which has the advantage that the fluid does not wet the electrical parts of the sensor. Here, two inductively-coupled coils are used. One is the driving coil producing a magnetic field and it is supplied with accurately-known voltage. The other forms a secondary coil of a transformer. The liquid passing through a channel in the sensor forms one turn in the secondary winding of the transformer. The induced current is the output of the sensor.

Temperature dependence:
Electrical conductivity The conductivity of a solution is highly temperature dependent, therefore it is important to either use a temperature compensated instrument, or calibrate the instrument at the same temperature as the solution being measured. Unlike metals, the conductivity of common electrolytes typically increases with increasing temperature. Over a limited temperature range, the way temperature affect conductivity of a solution can be modeled linearly using the following formula:

where T is the temperature of the sample, Tcal is the calibration temperature, T is the electrical conductivity at the temperature T, Tcal is the electrical conductivity at the calibration temperature Tcal, is the temperature compensation slope of the solution. The temperature compensation slope for most naturally occurring waters is about 2 %/C, however it can range between 1 to 3 %/C. The compensation slope for some common water solutions are listed in the table below. Aqueous solution at 25 C Concentration (mass percentage) (%/C) HCl 10 1.56 KCl 10 1.88 H2SO4 50 1.93 NaCl 10 2.14 HF 1.5 7.20 HNO3 31 31

Conductivity factor:
conductivity factor (CF) of dissolvedsalts in a given solution is a measurement of conductivity. Using the electrical conductivity between two electrodes in a water solution, the level of dissolved solids in that solution can be measured. Measurements can then be used to dose the solution with the necessary nutrients in the case of hydroponics. Conductivity measurements are also used in ecology and environmental sciences to assess the level of nutrients in lakes and rivers

Ultraviolet-visible spectroscopy or ultraviolet-visible spectrophotometers (UV-Vis or UV/Vis):

It refers to absorption spectroscopy or reflectance spectroscopy in the ultraviolet-visible spectral region. This means it uses light in the visible and adjacent (near-UV and nearinfrared (NIR)) ranges. The absorption or reflectance in the visible range directly affects the perceived color of the chemicals involved. In this region of the electromagnetic spectrum, molecules undergo electronic transitions. This technique is complementary to fluorescence spectroscopy, in that fluorescence deals with transitions from the excited state to the ground state, while absorption measures transitions from the ground state to the excited state. UV/Vis spectroscopy is routinely used in the quantitative determination of solutions of transition metal ions highly conjugatedorganic compounds, and biological macromolecules.

Solutions of transition metal ions can be colored (i.e., absorb visible light) because d electrons within the metal atoms can be excited from one electronic state to another. The colour of metal ion solutions is strongly affected by the presence of other species, such as certain anions or ligands. For instance, the colour of a dilute solution of copper sulfate is a very light blue; adding ammonia intensifies the colour and changes the wavelength of maximum absorption (max).

Organic compounds, especially those with a high degree of conjugation, also absorb light in the UV or visible regions of the electromagnetic spectrum. The solvents for these determinations are often water for water soluble compounds, or ethanol for organic-soluble compounds. (Organic solvents may have significant UV absorption; not all solvents are suitable for use in UV spectroscopy. Ethanol absorbs very weakly at most wavelengths.) Solvent polarity and pH can affect the absorption spectrum of an organic compound. Tyrosine, for example, increases in absorption maxima and molar extinction coefficient when pH increases from 6 to 13 or when solvent polarity decreases.

While charge transfer complexes also give rise to colours, the colours are often too intense to be used for quantitative measurement.

The Beer-Lambert law states that the absorbance of a solution is directly proportional to the concentration of the absorbing species in the solution and the path length. Thus, for a

fixed path length, UV/Vis spectroscopy can be used to determine the concentration of the absorber in a solution. It is necessary to know how quickly the absorbance changes with concentration. This can be taken from references (tables of molar extinction coefficients), or more accurately, determined from a calibration curve. A UV/Vis spectrophotometer may be used as a detector for HPLC. The presence of an analyte gives a response assumed to be proportional to the concentration. For accurate results, the instrument's response to the analyte in the unknown should be compared with the response to a standard; this is very similar to the use of calibration curves. The response (e.g., peak height) for a particular concentration is known as the response factor. The wavelengths of absorption peaks can be correlated with the types of bonds in a given molecule and are valuable in determining the functional groups within a molecule. The Woodward-Fieser rules, for instance, are a set of empirical observations used to predict max, the wavelength of the most intense UV/Vis absorption, for conjugated organic compounds such as dienes and ketones. The spectrum alone is not, however, a specific test for any given sample. The nature of the solvent, the pH of the solution, temperature, high electrolyte concentrations, and the presence of interfering substances can influence the absorption spectrum. Experimental variations such as the slit width (effective bandwidth) of the spectrophotometer will also alter the spectrum. To apply UV/Vis spectroscopy to analysis, these variables must be controlled or accounted for in order to identify the substances present.

Beer-Lambert law
The method is most often used in a quantitative way to determine concentrations of an absorbing species in solution, using the Beer-Lambert law: , Where A is the measured absorbance, I0 is the intensity of the incident light at a given wavelength, I is the transmitted intensity, L the path length through the sample, and c the concentration of the absorbing species. For each species and wavelength, is a constant known as the molar absorptivity or extinction coefficient. This constant is a fundamental molecular property in a given solvent, at a particular temperature and pressure, and has units of 1 / M * cm or often AU / M * cm. The absorbance and extinction are sometimes defined in terms of the natural logarithm instead of the base-10 logarithm. The Beer-Lambert Law is useful for characterizing many compounds but does not hold as a universal relationship for the concentration and absorption of all substances. A 2nd order polynomial relationship between absorption and concentration is sometimes encountered for very large, complex molecules such as organic dyes (Xylenol Orange or Neutral Red, for example).

Ultraviolet-visible spectrophotometer
The instrument used in ultraviolet-visible spectroscopy is called a UV/Vis spectrophotometer. It measures the intensity of light passing through a sample (I), and compares it to the intensity of light before it passes through the sample (Io). The ratio I / Iois called the transmittance, and is usually expressed as a percentage (%T). The absorbance, A, is based on the transmittance: A = log(%T / 100%) The UV-visible spectrophotometer can also be configured to measure reflectance. In this case, the spectrophotometer measures the intensity of light reflected from a sample (I), and compares it to the intensity of light reflected from a reference material (Io)(such as a

white tile). The ratio I / Iois called the reflectance, and is usually expressed as a percentage (%R). The basic parts of a spectrophotometer are a light source, a holder for the sample, a diffraction grating in a monochromator or a prism to separate the different wavelengths of light, and a detector. The radiation source is often a Tungsten filament (300-2500 nm), a deuterium arc lamp, which is continuous over the ultraviolet region (190-400 nm), Xenon arc lamps, which is continuous from 160-2,000 nm; or more recently, light emitting diodes (LED) [5] for the visible wavelengths. The detector is typically a photomultiplier tube, a photodiode, a photodiode array or a charge-coupled device(CCD). Single photodiode detectors and photomultiplier tubes are used with scanning monochromators, which filter the light so that only light of a single wavelength reaches the detector at one time. The scanning monochromator moves the diffraction grating to "step-through" each wavelength so that it's intensity may be measured as a function of wavelength. Fixed monochromators are used with CCDs and photodiode arrays. As both of these devices consist of many detectors grouped into one or two dimensional arrays, they are able to collect light of different wavelengths on different pixels or groups of pixels simultaneously.

Fig: Spectrophotometer

A spectrophotometer can be either single beam or double beam. In a single beam instrumentall of the light passes through the sample cell. Io must be measured by

removing the sample. This was the earliest design, but is still in common use in both teaching and industrial labs.

Diagram of a single-beam UV/Vis spectrophotometer. . In a double-beam instrument, the light is split into two beams before it reaches the sample. One beam is used as the reference; the other beam passes through the sample. The reference beam intensity is taken as 100% Transmission (or 0 Absorbance), and the measurement displayed is the ratio of the two beam intensities. Some double-beam instruments have two detectors (photodiodes), and the sample and reference beam are measured at the same time. In other instruments, the two beams pass through a beam chopper, which blocks one beam at a time. The detector alternates between measuring the sample beam and the reference beam in synchronism with the chopper. There may also be one or more dark intervals in the chopper cycle. In this case the measured beam intensities may be corrected by subtracting the intensity measured in the dark interval before the ratio is taken.

Diagram of double beam UV/VIS Spectrophotometer. Samples for UV/Vis spectrophotometry are most often liquids, although the absorbance of gases and even of solids can also be measured. Samples are typically placed in a transparent cell, known as a cuvette. Cuvettes are typically rectangular in shape, commonly with an internal width of 1 cm. (This width becomes the path length, L, in the Beer-Lambert law.) Test tubes can also be used as cuvettes in some instruments. The type of sample container used must allow radiation to pass over the spectral region of interest. The most widely applicable cuvettes are made of high quality fused silica or quartz glass because these are transparent throughout the UV, visible and near infrared regions. Glass and plastic cuvettes are also common, although glass and most plastics absorb in the UV, which limits their usefulness to visible wavelengths. Specialized instruments have also been made. These include attaching spectrophotometers to telescopes to measure the spectra of astronomical features. UVvisible microspectrophotometers consist of a UV-visible microscope integrated with a UV-visible spectrophotometer. These are commonly used for measuring thin film thickness in semiconductor manufacturing, materials science research, measuring the energy content of coal and petroleum source rock, and in forensic laboratories for the analysis of microscopic amounts of trace evidence as well as questioned documents. A complete spectrum of the absorption at all wavelengths of interest can often be produced directly by a more sophisticated spectrophotometer. In simpler instruments the absorption is determined one wavelength at a time and then compiled into a spectrum by

the operator. By removing the concentration dependence, the extinction coefficient () can be determined as a function of wavelength.

IR spectrophotometry
Spectrophotometers designed for the main infrared region are quite different because of the technical requirements of measurement in that region. One major factor is the type of photo sensors that are available for different spectral regions, but infrared measurement is also challenging because virtually everything emits IR light as thermal radiation, especially at wavelengths beyond about 5 m. Another complication is that quite a few materials such as glass and plastic absorb infrared light, making it incompatible as an optical medium. Ideal optical materials are salts, which do not absorb strongly. Samples for IR spectrophotometry may be smeared between two discs of potassium bromide or ground with potassium bromide and pressed into a pellet. Where aqueous solutions are to be measured, insoluble silver chloride is used to construct the cell. Sources An inert solid is electrically heated to a temperature in the range 1500-2000 K. The heated material will then emit infra red radiation. The Nernst glower is a cylinder (1-2 mm diameter, approximately 20 mm long) of rare earth oxides. Platinum wires are sealed to the ends, and a current passed through the cylinder. The Nernst glower can reach temperatures of 2200 K. The Globar source is a silicon carbide rod (5mm diameter, 50mm long) which is electrically heated to about 1500 K. Water cooling of the electrical contacts is needed to prevent arcing. The spectral output is comparable with the Nernst glower, execept at

The incandescent wire source is a tightly wound coil of nichrome wire, electrically heated to 1100 K. It produces a lower intensity of radiation than the Nernst or Globar sources, but has a longer working life.

Detectors There are three categories of detector;

Thermal Pyroelectric Photo conducting

Thermocouples consist of a pair of junctions of different metals; for example, two pieces of bismuth fused to either end of a piece of antimony. The potential difference (voltage) between the junctions changes according to the difference in temperature between the junctions Pyroelectric detectors are made from a single crystalline wafer of a pyroelectric material, such as triglycerine sulphate. The properties of a pyroelectric material are such that when an electric field is applied across it, electric polarization occurs (this happens in any dielectric material). In a pyroelectric material, when the field is removed, the polarization persists. The degree of polarization is temperature dependant. So, by sandwiching the pyroelectric material between two electrodes, a temperature dependant capacitor is made. The heating effect of incident IR radiation causes a change in the capacitance of the material. Pyroelectric detectors have a fast response time. They are used in most Fourier transform IR instruments. Photoelectric detectors such as the mercury cadmium telluride detector comprise a film of semiconducting material deposited on a glass surface, sealed in an evacuated envelope. Absorption of IR promotes nonconducting valence electrons to a higher, conducting, state. The electrical resistance of the semiconductor decreases. These detectors have better response characteristics than pyroelectric detectors and are used in FT-IR instruments - particularly in GC - FT-IR. Pneumatic detector A pressure-sensitive detectorbased on the pressure increase of a gas. A special type is the Golay cell where the pressure change is detected by observing the deflection off one of the chamber walls.

Types of instrument Dispersive infra red spectrophotometers These are often double-beam recording instruments, employing diffraction gratings for dispersion of radiation. Radiation from the source is flicked between the reference and sample paths. Often, an optical null system is used. This is when the detector only responds if the intensity of the two beams is unequal. If the intensities are unequal, a light attenuator restores equality by moving in or out of the reference beam. The recording pen is attached to this attenuator. Fourier-transform spectrometers Any waveform can be shown in one of two ways; either in frequency domain or time domain.

Dispersive IR instruments operate in the frequency domain. There are, however, advantages to be gained from measurement in the time domain followed by computer transformation into the frequency domain. If we wished to record a trace in the time domain, it could be possible to do so by allowing radiation to fall on a detector and recording its response over time. In practice, no detector can respond quickly enough (the radiation has a frequency greater than 1014 Hz). This problem can be solved by using interference to modulate the i.r. signal at a detectable frequency. The Michelson interferometer is used to produce a new signal of a much lower frequency which contains the same information as the original IR signal. The output from the interferometer is an interferogram.

The Michelson interferometer

Radiation leaves the source and is split. Half is reflected to a stationary mirror and then back to the splitter. This radiation has travelled a fixed distance. The other half of the radiation from the source passes through the splitter and is reflected back by a movable mirror. Therefore, the path length of this beam is variable. The two reflected beams recombine at the splitter, and they interfere (e.g. for any one wavelength, interference will be constructive if the difference in path lengths is an exact multiple of the wavelength. If the difference in path lengths is half the wavelength then destructive interference will result). If the movable mirror moves away from the beam splitter at a constant speed, radiation reaching the detector goes through a steady sequence of maxima and minima as the interference alternates between constructive and destructive phases. If monochromatic IR radiation of frequency, f ( ir ) enters the interferometer, then the output frequency, fm can be found by;

Wherev is the speed of mirror travel in mm/s Because all wavelengths emitted by the source are present, the interferogram is extremely complicated. The moving mirror must travel smoothly; a frictionless bearing is used with electromagnetic drive. The position of the mirror is measured by a laser shining on a

corner of the mirror. A simple sine wave interference pattern is produced. Each peak indicates mirror travel of one half the wavelength of the laser. The accuracy of this measurement system means that the IR frequency scale is accurate and precise. In the FT-IR instrument, the sample is placed between the output of the interferometer and the detector. The sample absorbs radiation of particular wavelengths. Therefore, the interferogram contains the spectrum of the source minus the spectrum of the sample. An interferogram of a reference (sample cell and solvent) is needed to obtain the spectrum of the sample. After an interferogram has been collected, a computer performs a Fast Fourier Transform, which results in a frequency domain trace (i.e. intensity vs. wave number) that we all know and love. The detector used in an FT-IR instrument must respond quickly because intensity changes are rapid (the moving mirror moves quickly). Pyroelectric detectors or liquid nitrogen cooled photon detectors must be used. Thermal detectors are too slow. To achieve a good signal to noise ratio, many interferograms are obtained and then averaged. This can be done in less time than it would take a dispersive instrument to record one scan. Advantages of Fourier transform IR over dispersive IR;

Improved frequency resolution Improved frequency reproducibility (older dispersive instruments must be recalibrated for each session of use)

Higher energy throughput Faster operation Computer based (allowing storage of spectra and facilities for processing spectra) Easily adapted for remote use (such as diverting the beam to pass through an external cell and detector, as in GC - FT-IR)

GAS CHROMATOGRAPHY Introduction Gas chromatography - specifically gas-liquid chromatography - involves a sample being vaporized and injected onto the head of the chromatographic column. The sample is transported through the column by the flow of inert, gaseous mobile phase. The column itself contains a liquid stationary phase which is adsorbed onto the surface of an inert solid. Have a look at this schematic diagram of a gas

Gas chromatography (GC), is a common type of chromatography used in analytic chemistry for separating and analyzing compounds that can be vaporized without decomposition. Typical uses of GC include testing the purity of a particular substance, or separating the different components of a mixture (the relative amounts of such components can also be determined). In some situations; GC may help in identifying a compound. In preparative chromatography, GC can be used to prepare pure compounds from a mixture. In gas chromatography, the moving phase (or "mobile phase") is a carrier gas, usually an inert gas such as helium or an unreactive gas such as nitrogen. The stationary phase is a microscopic layer of liquid or polymer on an inert solid support, inside a piece of glass or metal tubing called a column (a homage to the column used in distillation).

The instrument used to perform gas chromatography is called a gas chromatograph (or "aerograph", "gas separator"). The gaseous compounds being analyzed interact with the walls of the column, which is coated with different stationary phases. This causes each compound to elute at a different time, known as the retention time of the compound. The comparison of retention times is what gives GC its analytical usefulness. Gas chromatography is in principle similar to column chromatography (as well as other forms of chromatography, such as HPLC, TLC), but has several notable differences. Firstly, the process of separating the compounds in a mixture is carried out between a liquid stationary phase and a gas moving phase, whereas in column chromatography the stationary phase is a solid and the moving phase is a liquid. (Hence the full name of the procedure is "Gas-liquid chromatography", referring to the mobile and stationary phases, respectively.) Secondly, the column through which the gas phase passes is located in an oven where the temperature of the gas can be controlled, whereas column chromatography (typically) has no such temperature control. Thirdly, the concentration of a compound in the gas phase is solely a function of the vapor pressure of the gas.[1] Gas chromatography is also similar to fractional distillation, since both processes separate the components of a mixture primarily based on boiling point (or vapor pressure) differences. However, fractional distillation is typically used to separate components of a mixture on a large scale, whereas GC can be used on a much smaller scale (i.e. micro scale). Gas chromatography is also sometimes known as vapor-phase chromatography (VPC), or gas-liquid partition chromatography (GLPC). These alternative names, as well as their respective abbreviations, are frequently found in scientific literature. Strictly speaking,

The Modern Gas Chromatograph The modern gas chromatograph is a fairly complex instrument mostly computer controlled. The samples are mechanically injected, the analytical results are automatically calculated and the results printed out, together with the pertinent operating conditions in a standard format. However, the instrument has evolved over many years although the majority of the added devices and techniques were suggested or describe in the first three international symposia on gas chromatography held in 1956, 1958 and 1960. These symposia, initially organized by the 'British Institute of Petroleum' have been held every two years ever since 1956 and the meetings have remained the major stimulus for developing the technique and extending its capabilities. However, the majority of the techniques and devices that have been incorporated in the modern chromatograph, were described, reported, or discussed in the first triad of symposia.

The layout of the modern gas chromatograph is shown as a block diagram in figure 1.

Instrumental components Carrier gas The carrier gas must be chemically inert. Commonly used gases include nitrogen, helium, argon, and carbon dioxide. The choice of carrier gas is often dependent upon the type of detector which is used. The carrier gas system also contains a molecular sieve to remove water and other impurities. Injection Devices The basic injection devices that are used in chromatography, such as the external loop valve, have been discussed in book 1. In gas chromatography two basic types of sampling system are used, those suitable for packed columns and those designed for open tubular columns. In addition, different sample injectors are necessary that will be appropriate for alternative column configurations. It

must be stressed, however, that irrespective of the design of the associated equipment, the precision and accuracy of a GC analysis will only be as good as that provided by the sample injector. The sample injector is a very critical part of the chromatographic equipment and needs to be well designed and well maintained.

Sample injection port For optimum column efficiency, the sample should not be too large, and should be introduced onto the column as a "plug" of vapor - slow injection of large samples causes band broadening and loss of resolution. The most common injection method is where a micro syringe is used to inject sample through a rubber septum into a flash vaporizer port higher than the boiling point of the least volatile component of the sample. For packed columns, sample size ranges from tenths of a micro liter up to 20 micro liters. Capillary columns, on the other hand, need much less sample, typically around 10-3 capillary GC, split/split less injection is used. Have a look at this diagram of a split/split less injector;

The injector can be used in one of two modes; split or split less. The injector contains a heated chamber containing a glass liner into which the sample is injected through the septum. The carrier gas enters the chamber and can leave by three routes (when the injector is in split mode). The sample vaporizes to form a mixture of carrier gas, vaporized solvent and vaporized solutes. A proportion of this mixture passes onto the column, but most exits through the split outlet. The septum purge outlet prevents septum bleed components from enter the column.

Open Tubular Column Injection Systems Due to the very small sample size that must be placed on narrow bore capillary columns, a split injection system is necessary.

The basic difference between the two types of injection systems is that the capillary column now projects into the glass liner and a portion of the carrier gas sweeps past the column inlet to waste. As the sample passes the column opening, a small fraction is split off and flows directly into the capillary column, ipso facto this device is called a split injector. The split ratio is changed by regulating the portion of the carrier gas that flows to waste which is achieved by an adjustable flow resistance in the waste flow line. This device is only used for small diameter capillary columns where the charge size is critical.

Columns There are two general types of column, packed and capillary (also known as open tubular). Packed columns contain a finely divided, inert, solid support material (commonly based on diatomaceous earth) coated with liquid stationary phase. Most packed columns are 1.5 - 10m in length and have an internal diameter of 2 - 4mm. Capillary columns have an internal diameter of a few tenths of a millimeter. They can be one of two types; wall-coated open tubular (WCOT) or support-coated open tubular (SCOT). Wall-coated columns consist of a capillary tube whose walls are coated with liquid stationary phase. In support-coated columns, the inner wall of the capillary is lined with a thin layer of support material such as diatomaceous earth, onto which the stationary phase has been adsorbed. SCOT columns are generally less efficient than WCOT columns. Both types of capillary column are more efficient than packed columns. In 1979, a new type of WCOT column was devised - the Fused Silica Open Tubular (FSOT) column;

These have much thinner walls than the glass capillary columns, and are given strength by the polyimide coating. These columns are flexible and can be wound into coils. They have the advantages of physical strength, flexibility and low reactivity. The Packed GC Column Packed columns are usually constructed from stainless steel or Pyrex glass. Pyrex glass is favored when thermally labile materials are being separated such as essential oils and flavor components. However, glass has pressure limitations and for long packed columns, stainless steel columns are used as they can easily tolerate the necessary elevated pressures. The sample must, of course, be amenable to contact with hot metal surfaces. Short columns can be straight, and installed vertically in the chromatograph. Longer columns can be U-shaped but columns more than a meter long are usually coiled. Such columns can be constructed of any practical length and relatively easily installed. Pyrex glass columns are formed to the desired shape by coiling at about 700C and metal columns by bending at room temperature. Glass columns are sometimes treated with an appropriate silanizing reagent to eliminate the surface hydroxyl groups which can be catalytically active or produce asymmetric peaks. Stainless steel columns are usually washed with dilute hydrochloric acid, then extensively with water followed by methanol, acetone, methylene dichloride and n-hexane. This washing procedure removes any corrosion products and traces of lubricating agents used in the tube drawing process. The columns are then ready for packing.

Column temperature For precise work, column temperature must be controlled to within tenths of a degree. The optimum column temperature is dependent upon the boiling point of the sample. As a rule of thumb, a temperature slightly above the average boiling point of the sample results in an elution time of 2 - 30 minutes. Minimal temperatures give good resolution, but increase elution times. If a sample has a wide boiling range, then temperature programming can be useful. The column temperature is increased (either continuously or in steps) as separation proceeds.

Detectors There are many detectors which can be used in gas chromatography. Different detectors will give different types of selectivity. A non-selective detector responds to all

compounds except the carrier gas, a selective detector responds to a range of compounds with a common physical or chemical property and a specific detector responds to a single chemical compound. Detectors can also be grouped into concentration dependant detectors and mass flow dependant detectors. The signal from a concentration dependant detector is related to the concentration of solute in the detector, and does not usually destroy the sample Dilution of with make-up gas will lower the detectors response. Mass flow dependant detectors usually destroy the sample, and the signal is related to the rate at which solute molecules enter the detector. The response of a mass flow dependant detector is unaffected by make-up gas. Have a look at this tabular summary of common GC detectors: Detector Flame ionization (FID) Type Mass flow Support gases Hydrogen and air Selectivity Most organic cpds. Detectability 100 pg Dynamic range 107

Thermal conductivity Concentration Reference (TCD) Electron capture (ECD) Nitrogenphosphorus Flame photometric (FPD) Concentration Make-up Hydrogen and air Hydrogen and air possibly oxygen

Universal

1 ng

107

Halides, nitrates, nitriles, peroxides, 50 fg anhydrides, organometallics Nitrogen, phosphorus 10 pg Sulphur, phosphorus, tin, boron, arsenic, 100 pg germanium, selenium, chromium Aliphatics, aromatics, ketones, esters, aldehydes, amines, 2 pg heterocyclics, organosulphurs, some organometallics Halide, nitrogen, nitrosamine, sulphur

105

Mass flow

106

Mass flow

103

Photoionization (PID)

Concentration Make-up

107

Hall electrolytic Mass flow conductivity

Hydrogen, oxygen

The effluent from the column is mixed with hydrogen and air, and ignited. Organic compounds burning in the flame produce ions and electrons which can conduct electricity through the flame. A large electrical potential is applied at the burner tip, and a collector electrode is located above the flame. The current resulting from the pyrolysis of any organic compounds is measured. FIDs are mass sensitive rather than concentration sensitive; this gives the advantage that changes in mobile phase flow rate do not affect the detector's response. The FID is a useful general detector for the analysis of organic compounds; it has high sensitivity, a large linear response range, and low noise. It is also robust and easy to use, but unfortunately, it destroys the sample The Nitrogen Phosphorus Detector (NPD)

The nitrogen phosphorus detector (NPD), is a highly sensitive but specific detector and evolved directly from the FID. It gives a strong response to organic compounds containing nitrogen and/or phosphorus. Although it appears to function in a very similar manner to the FID, in fact, it operates on an entirely different principle. A diagram of an NP detector is shown in figure 24.

The Electron Capture Detector The electron capture detector contains a low energy source which is used to produce electrons for capturing by appropriate atoms. Although tritium adsorbed into a silver foil has been used as the particle source, it is relatively unstable at high temperatures, the Ni63 source was found to be preferable. The detector can be used in two modes, either with a constant potential applied across the cell (the DC mode) or with a pulsed potential across the cell (the pulsed mode). In the DC mode, hydrogen or nitrogen can be used as the carrier gas and a small potential (usually only a few volts) is applied across the cell that is just sufficient to collect all the electrons available and provide a small standing current. If an electron capturing molecule (for example a molecule containing an halogen atom which has only seven electrons in its outer shell) enters the cell, the electrons are captured by the molecule and the molecules become charged. The mobility of the captured electrons is much smaller than the free electrons and the electrode current falls dramatically. The DC mode of detection, however, has some distinct disadvantages. The most serious objection is that the electron energy varies with the applied potential. The electron capturing properties of a molecule varies with the electron energy, so the specific response of the detector will depend on the applied potential Operating in the pulsed mode, a mixture of 10% methane in argon is employed which changes the nature of the electron capturing environment. The electrons generated by the radioactive source rapidly assume only thermal energy and, in the absence of a collecting potential, exist at the source surface in an annular region about 2 mm deep at room temperature and about 4 mm deep at 400C. A short period square wave pulse is applied to the electrode collecting the electrons and producing a base current. The standing current, using 10% methane in argon is about 10-8 amp with a noise level of about 5 x 10-12 amp. The pulse wave form is shown in figure

Wave form of Electron Capture Detector Pulses In the inactive period of the wave form, electrons having thermal energy only will attached themselves readily to any electron capturing molecules present in the cell with the consequent production of negatively charged ions. The negative ions quickly recombine with the positive ions and thus become unavailable for collection. Consequently the standing current measured during the potential pulse will be reduced. The period of the pulsed potential is adjusted such that relatively few of the slow negatively charged molecules (molecules having captured electrons and not neutralized by collision with positive ions) have time to reach the anode, but the faster moving electrons are all collected. During the "off period" the electrons re-establish equilibrium with the gas. The three operating variables are the pulse duration, pulse frequency and pulse amplitude. By appropriate adjustment of these parameters the current can be made to reflect the relative mobilities of the different charged species in the cell and thus exercise some discrimination between different electron capturing materials. A diagram of an electron capture detector is shown in fig.

Electron Capture Detector

Gas Supplies Gases for use with the gas chromatograph were originally all obtained from gas tanks or gas cylinders. However, over the past decade the use of gas generators have become more popular as it avoids having gases at high pressure in the laboratory which is perceived by some as potentially dangerous. In addition, the use of a hydrogen generator avoids the use of a cylinder of hydrogen at high pressure which is also perceived by some as a serious fire hazard despite the fact that they have been used in laboratories, quite safely for nearly a century. Supplies from Gas Tanks Gasses are stored in large cylindrical tanks fitted with reducing valves that are set to supply the gas to the instrument at the recommended pressure defined by the manufacturers. The cylinders are often situated outside and away from the chromatograph for safety purposes and the gasses are passed to the chromatograph through copper or stainless steel conduits at relatively low pressure. The main disadvantage of gas tanks is their size and weight which makes them difficult to move and replace.

Pure Air Generators. Air generators require an air supply from air tanks or directly from the laboratory compressed air supply. The Packard Zero Air Generator passes the gas through a 0.5filter to remove oil and water and finally over a catalyst to remove hydrocarbons. The hydrocarbon free air is then passed through a 0.01 cellulose fiber filter to remove any residual particulate matter that may be present. The manufacturers claim the resulting air supply contains less than 0.1 ppm total hydrocarbons and delivers air at 125 psi at flow rates up to 2,500 cc per min. Preparative Gas Chromatography Gas chromatography has not been used extensively for preparative work although its counterpart, liquid chromatography, has been broadly used in the pharmaceutical industry for the isolation and purification of physiologically active substances. There are a number of unique problems associated with preparative gas chromatography. Firstly, it is difficult to recycle the mobile phase and thus large volume of gas are necessary. Secondly, the sample must be fully vaporized onto the column to ensure radial distribution of the sample across the column. Thirdly, the materials of interest are eluted largely in a very dilute form from the column and therefore must be extracted or condensed from the gas stream which is also difficult to achieve efficiently. Finally, the efficient packing of large GC columns is difficult. Nevertheless, preparative GC has been successfully used in a number of rather special applications; for example the isolation of significant quantities of the trace components of essential oils for organoleptic assessment. The layout of a preparative gas chromatograph is shown in figure38

Figure 38 Layout of Preparative Gas Chromatograph Air cannot normally be used as the mobile phase due to likely oxidation and so either a gas tank or a gas (e.g., nitrogen) generator must be used. As the flow rates can be large, more than one generator operating in parallel will often be necessary. The sample is usually placed on to the column with a syringe pump and rapidly vaporized in a suitable heater. Passing the gas in vapor form onto the column helps evenly distribute the sample radially across the column. The detector that is used must have specifications that are almost opposite to those of an analytical detector. It should function well at high concentrations of solute, have a generally low sensitivity, if in-line it must be non-destructive and have minimum flow impedance. It need not have a particularly linear response. The katharometer is one of the more popular detectors for preparative GC. The column outlet is passed to a selection valve that diverts the eluent to its appropriate collecting vessel. The collecting vessel may be cooled in ice, solid carbon dioxide or if necessary liquid nitrogen (liquid nitrogen can only be used if a low boiling gas such as helium is employed as the carrier gas). In some cases the solutes contained in the eluent can be extracted into an appropriate liquid or onto the surface of a suitable adsorbent. the desired fractions are then recovered by distillation or desorption.

The Moving Bed Continuous Chromatography System The concept of the moving bed extraction process was originally introduced for hydrocarbon gas adsorption by Freund et al. (13) and was first applied to gas liquid chromatography by Scott (14). A diagram of the moving bed system suitable for GC was proposed by Scott and is shown in figure 39.

The feasibility of this process was established for a gas chromatographic system, subsequently, its viability was also confirmed for liquid chromatography which will be discussed in Book 19. The moving bed system takes a continuous sample feed and operates in the following way. The stationary phase, coated on a suitable support, is allowed to fall down a column against and upward stream of carrier gas. In the original device of Scott, the packing (dinonyl phthalate coated on brick dust) was contained in a hopper at the top of the column and was taken off from the bottom the column by a rotating disc feed table and returned to the hopper by a simple air-lift device.

Courtesy of Butterworths Scientific Publications Ltd. [Ref. 10]

Applications Gas chromatography has a very wide field of application but its first and main area of use is in the separation and analysis of multi component mixtures such as essential oils, hydrocarbons and solvents. Intrinsically, with the use of the flame ionization detector and the electron capture detector (which have very high sensitivities) gas chromatography can quantitatively determine materials present at very low concentrations. It follows, that the second most important application area is in pollution studies, forensic work and general trace analysis. Gasoline Gasoline is a multicomponent mixture containing a large number of hydrocarbons, many of which have very similar molecular weights and all are almost exclusively dispersive in interactive character. The structures of many of the hydrocarbons are also very similar and there are many isomers present. As a consequence, due to their interactive similarity the separation factors between individual components are very small.

It follows that columns of very high efficiency will be mandatory to achieve an effective separation. It is clear that open tubular columns are ideal for this type of separation problem. In fact, it would be impossible to separate the components of gasoline efficiently with a packed column, even one that is 50 ft long, and even if the inherent long analysis times could be tolerated. In addition this type of separation demands the maximum number of theoretical plates and therefore not only must open tubes be used but tubes of relatively small diameter to produce the maximum number of theoretical plates. In fact, several hundred thousand theoretical plates will be necessary and so the column must also be very long. As has already been discussed, it is necessary to use small radius open tubular columns with a split injection system. Furthermore, as a result of the wide range of molecular weight of the components present, gasoline has a relatively wide boiling range and so will require a temperature program that will heat the column to 200 C or more. A thermally stable stationary phase must be employed.The individual gasoline components are present over a wide concentration range and thus, for accurate quantitative results, the linear dynamic range of the detector must also be large. These latter demands mandate that the detector must be the FID.

Food and Beverage Products

Due to the likely contamination of food and beverage products with pesticides, herbicides and many other materials that are considered a health risk, all such products on sale today must be carefully assayed. There is extensive legislation controlling the quality of all human foods and drinks, and offensives carry very serious penalties. In addition, the condition of the food is also of great concern to the food chemist, who will look for those trace materials that have been established to indicate the onset of bacterial action, aging, rancidity or decomposition. In addition, tests that identify the area or country in which the food was processed or grown may also be needed. The source of many plants (herbs and spices) can often be identified from the peak pattern of the chromatograms obtained directly from headspace analysis. Similarly, unique qualitative and quantitative patterns from a GC analysis will often help identify the source of many alcoholic beverages. Unfortunately, food analysis involves the separation and identification of very complex mixtures and the difficulties are compounded by the fact that the components are present at very low concentrations. Thus, gas chromatography is the ideal (if not only) technique that can be used successfully in food and beverage assays and tests. The potential carcinogenity of the aromatic hydrocarbons make their separation and analysis extremely important in environmental testing. However, the aromatics can pose some serious separation problems (for example, the mand p-xylenes) due to the closely similar chemical structure and characteristics. The xylene isomers differ in structure (although not optically active) have similar spatial differences to pairs of enantiomers. It follows, chiral stationary phases that separate enantiomers can also be used for separating spatial isomers that are not necessarily optically active. Nevertheless, the separation ratios of such isomeric pairs (even on cyclodextrin stationary phases) is still very small, often in the 1.021.03 range. As a consequence, the use of high efficiency

capillary columns is essential, if reasonable analysis times are also to be maintained.

Introduction Liquid chromatography (LC) was the first type of chromatography to be discovered and, in the form of liquid-solid chromatography (LSC), was originally used in the late 1890s by the Russian botanist, Tswett (1), to separate and isolate various plant pigments. The colored bands he produced on the adsorbent bed evoked the term chromatography (color writing) for this type of separation. Initially the work of Tswett was not generally accepted, partly due to the original paper being in Russian and thus, at that time, was not readily available to the majority of western chemists and partly due to the condemnation of the method by Willstatter and Stoll (2) in 1913. Willstatter and Stoll repeated Tswett's experiments without heeding his warning not to use too "aggressive adsorbents as these would cause the chlorophylls to decompose. As a consequence, the experiments of Willstatter et al. failed and their published results, rejecting the work of Tswett, impeded the recognition of chromatography as a useful separation technique for nearly 20 years. In the late 1930s and early 1940s Martin and Synge introduced a form of liquid-liquid chromatography by supporting the stationary phase, in this case water, on silica gel in the form of a packed bed and used it to separate some acetyl amino acids. They published their work in 1941 (3) and in their paper recommended the replacement of the liquid mobile phase with a suitable gas, which would accelerate the transfer between the two phases and provide more efficient separations. Thus, the concept of gas chromatography was born. In the same paper in 1941, Martin and Synge suggested the use of small particles and high pressures in LC to improve the separation that proved to the critical factors that initiated the development of high performance liquid chromatography.

The statement made by Martin in 1941 contains all the necessary conditions to realize both the high efficiencies and the high resolution achieved by modern LC columns. Despite his recommendations, however, it took nearly fifty years to bring his concepts to fruition. Activity in the field of liquid chromatography was eclipsed in the 1950s by the introduction of gas chromatography and serious attempts were not made to improve LC techniques until the development of GC neared completion in the mid 1960s. The major impediment to the development of LC was the lack of a high sensitive detector and it was not until the refractive index detector was developed by A. Tiselius and D. Claesson (4) in 1942 could the technique be effectively developed. Tswett's original LC consisted of a vertical glass tube, a few centimetres in diameter and about 30 cm high, packed with the adsorbent (calcium carbonate). The plant extract pigments were placed on the top of the packing and the mobile phase carefully added to fill the tube. The solvent percolated through the packing under gravity, developing the separation, which could be seen as different colored bands at the wall of the tube. The simple apparatus of Tswett contained all the essentials to achieve a chromatographic separation. The contemporary chromatograph, however, is a very complex instrument operating at pressures up to 10,000 p.s.i providing flow rates ranging from a few microliters per minute to 10 or 20 ml/minute depending on the type of LC that is carried out. Modern detectors can detect solutes at concentration levels of 1x10-9 g/ml and an analysis can be completed in a few minutes with just a few micrograms of sample.

CO Monitoring:
Co monitoring consisting of two methods: 1. Chromatographic technique 2. Infrared method

Chromatographic Technique:
--It's range is 0-200ppm --Sensitivity 0.1ppm Diagram:

Theory:
--Any series

of copound which has high or regionalblevapour pressure can be supperated by gas chromatograph. --This is useful for supperation of Hydrogen,Carbon,Nytrogen and other organic compounds. --In this sample and air contains CO is passed through stripped column or pre-column then heavy hydro carbon are retainetheir,other than CH4,CO. --These are passed into the chromatographic column, and then toacatelic chamber and here the CO is reduced to methene(CH4).Which is detected by flame ionization detector from which peaks are obtain in which the 1st peak corresponds to CH4 and 2nd corresponds to CO. Advantages: --Its an accurate. --Highly Sensitive --It can also measure CH4(Methene). Disadvantages: --It is expensive and complex.

Infrared Method:
--This is uasally range of 0-25,50,100 ppm levels. Diagram:

Advantages: --Highly accurate and stable. Disadvantages: --It is Sensitive.

NOx Analyzers:
If detection of nitric oxide is important to your research, have you thought of detecting nitrite, which can bring you more insight? The detection of nitric oxide (NO) in biological liquid samples is extremely difficult due to the transient half-life of NO molecules. Some report the biological lifetime to be in the order of milliseconds. Once you remove the sample from the animal or other source, it is almost impossible to directly detect nitric oxide. Thus, detection of nitrite and nitrate, considered to be the major metabolites of NO, can be used to determine the NO levels. Moreover, if you evaluate the nitric oxide level with an in-vivo sensing procedure, it shows only one aspect of the nitric oxide profile. Monitoring nitrite level has become increasingly important in recent years. Studies have shown nitrite to be indirectly related to physiological activity and it is also a signaling molecule. The ENO-20s high sensitivity and specificity are accomplished with the combination of a dizao coupling method and chromatography. Nitrite and nitrate are separated from other substances on a unique separation column and mobile phase. Nitrite then reacts with a compound called Griess reagent and generates diazo compounds which have a red color. The level of nitrite can be monitored with peak height or area with a retention time of 4.5 min from the injection of the sample. Nitrate is reduced to nitrite on a reduction column which reacts to the Griess reagent as well. The nitrate peak has an 8

min retention time. The level of diazo compound is measured by absorbance at 540 nm using a visible detector. The separation column is robust as well as the entire ENO-20. Normal lifetime of the column is at least 3 months with regular use. All separation and detection technologies are provided by Eicom for the ENO-20 including mobile phase ingredients, Greiss reagent, separation columns, and reduction columns. You can relax and detect nitrite and nitrate with 10 nM sensitivity (0.1 pmol)

Nox analyzers are classified into three types: They are 1. Laser opto acoustic spectroscopy 2. Chemiluminescence method 1. Laser opto acoustic spectroscopy: Radiation source can be output from a laser, a monochromator furnishing radiations in UV, IR, or a FT-IR spectrometer. All radiation must be pulsed at an acoustical frequency 50-1200Hz. PA cell is filled with transparent gas often air or helium and cell volume is kept small, less than 1cm3 in order to preserve the strength of the acoustical signal.

Fig:1 One main advantage of opto acoustic spectroscopy is the ability to get information about the depth in the sample of the absorption. The amount of the sample contributing to the PA signal is proportional to the thermal diffusion depth. This thermal diffusion depth , is inversely proportional to the modulation frequency f. Figure 3 shows a model sample that has a thermally thin surface layer (thickness << ) on a bulk substrate. After the light has been absorbed, the heat has to diffuse from the point of absorption to the surface of the sample to be detected. Since this thermal diffusion is a slow process

relative to the light absorption and non- radiative decay, an absorption in the bulk will have a phase lag between the time of absorption and the thermal signal. However, a surface absorption should not have a phase lag since the heat doesn't have far to travel to generate the detected pressure change in the transfer gas.

Fig 2

Advantages:

The sample does not have to be dissolved in some solvent or embedded in a solid matrix, it is to be used as its. Conventional absorption spectroscopy is based on excitation by electromagnetic radiation with intensity I and the measurement of reflected or transmitted light intensity I. Thus, the absorbencies derived indirectly from transmittance or reflectance, whereas in PAS pressure waves are detected which are generated directly by the absorbed energy. PA signal is not influenced by the scattering particles. PAS allows the determination of absorption coefficients over several orders of magnitude. This analytical technique can be applied to the measurement of weak absorption using PA cells with relatively small path lengths, allowing compact and mobile set-ups PA signal depends on the incident radiation power hence the sensitivity can be tuned to desired range by choosing an appropriate radiation source (for example, a lamp versus a laser). PAS is useful for sample that are powered, amorphous or otherwise not conductive to reflective or transmission form of optical spectroscopies.

2.Chemiluminescence method and Catalytic thermal decomposition: Sample is reacted with oxygen using oxidation catalyst to transform the nitrogen compounds into nitric monoxide (nitrogen and nitrogen dioxide do not transform to nitric monoxide). When nitric monoxide is reacted with ozone, nitrogen dioxide in semi-stable status is produced. When the nitrogen dioxide in semi-stable status changes into stable nitrogen dioxide, it emits lights and the strength of the light is in proportional to the concentration of nitric monoxide. Thus the total nitrogen concentration in the sample is identified by measuring the strength of the light. An example of total nitrogen analyzer using catalytic thermal decomposition and chemiluminescences method is illustrated below. Sample is weighed and then put into combustion tube, where the sample is heated to a high temperature and oxidized with oxidation catalyst into nitric monoxide. After

oxidation, the sample is dehumidified with a dryer and fed into the detector, where the sample is reacted with ozone as below. NO + O3 --> NO2 + O2 + h The strength of light of wavelength of 590 to 2500nm is measured.

Fig 3 (a).120C decomposition and UV absorptiometery: Add alkali solution of potassium peroxodisulfate to the sample and heat the mixture to approx. 120C to transform all the nitrogen compounds to nitric acid ions. Control the pH of this solution to 2 to 3 using hydrochloric acid, and measure the absorption of nitric acid ions in UV zone to obtain the total nitrogen concentration. An example of total nitrogen analyzer using 120C decomposition and UV absorptiometer is illustrated below. Sample is weighed and put into the sample water container. Specified amount of potassium peroxodisulfate and sodium hydroxide solutions are added to the sample, and the mixture is put into the thermal decomposition chamber. In the chamber, the mixture is heated at 120C for 30 minutes to oxidize the nitrogen compounds into nitric acid ions. The solution after the decomposition is put into reaction-cooling chamber to cool off. The cooled solution is then adjusted to pH 2-3 by adding hydrochloric acid. The absorbency of nitric acid ions in the solution is measured using UV absorptiometer at a wavelength of 220nm.

Example of total nitrogen analyzer of 120C decomposition- UV absorptiometery

Fig.4 (b) Photo oxidation decomposition and UV absorptiometery: Add alkali solution of potassium peroxodisulfate to the sample and radiate ultraviolet ray to transform all the nitrogen compounds to nitric acid ions. Control the pH of this solution to 2 to 3 using hydrochloric acid, and measure the absorption of nitric acid ions in UV zone to obtain the total nitrogen concentration. An example of total nitrogen analyzer using photooxidation and UV absorptiometer is illustrated below. Sample is weighed and put into the mixing chamber. Specified amount of potassium peroxodisulfate and sodium hydroxide solutions are added to the sample, and the mixture is put into the UV oxidation apparatus. In the chamber, the mixture is heated at 90C and exposed to ultraviolet ray for 15 minutes to oxidize the nitrogen compounds into nitric

acid ions. The solution after the decomposition is weighed and then adjusted to pH 2-3 by adding hydrochloric acid. The absorbency of nitric acid ions in the solution is measured using UV absorptiometer at a wavelength of 220nm. Example of total nitrogen analyzer of photooxidation decomposition- UV absorptiometery:

Fig.5 Advantage of Chemiluminescences method: Nitric oxide and ozone react in the gaseous phase to produce chemical luminescence. It is possible to detect nitrite in the liquid phase using this procedure but it is not as simple as using the ENO-20. What types of samples require the nitrite assay? Usually the sample matrix is liquid; the ENO-20 is the perfect device for this. In the process of reducing nitrite/nitrate, the system is heated which results in condensation on the inner surface of the glassware after cooling down. The condensation dissolves the nitrite/nitrate and will have an effect on carry-over when the condensation evaporates during the next process. This is a common reason for variation in the detected values of nitrite using the chemiluminescense procedure. As explained above, the ENO20 installed with an autosampler yields hands free analysis. You do not need to clean the glassware of the detection system following the analysis of several samples or following the sample conversion from liquid to gas.

H2S Analyzer Sample System THE NEED A critical measurement of natural gas quality is theconcentration of hydrogen sulfide (H2S). Remarkably,thecommon technique for making this measurement, leadacetate tape, is at least 70 years old. Users of this archaictechnology report general dissatisfaction with it due to high maintenances, the cost and shelf life of tape cassettes, the need for reagents, difficulty handling H2S overload conditions, the sensitivity of the technology to ambientextremes, and, not least, used cassette disposal. AMETEK Western Research has responded to the needfor a low maintenance, reliable, and rugged H2S analyzer by developing the Model 933. The Model 933 uses AMETEKWestern Researchs proprietary frontal elution chromatography sampling technique, combined with our exceptionally high resolution multi-wavelength UV optical bench. The result is a unique low level H2S analyzer that is designed to operate unattended for six months or more. THE MEASUREMENT AMETEK Western Research's unique sample conditioningsystem uses frontal elution chromatography to separate andeliminate interfering species. This ensures an accurateanalysis of the gas via direct-UV absorption spectroscopy.In sales gas applications, H2S and COS are the first absorbingspecies to elute through the chromatography column. Thesecompounds are analyzed photo metrically. The next species toelute is methyl mercaptan, which is also measured, and finally, the interfering ethyl mercaptan. Interference by ethyl mercaptan is prevented by terminating the sample analysis before itelutes, and then switching to a fresh column so that theanalysis may continue. Two columns are employed in 933.While one column is conditioning the gas sample, the other isautomatically regenerated. In normal operation, the 933 uses its analysis of the COS and methyl mercaptan oncentrations to provide real timecompensation for the H2S measurement. Optionally, the 933 can be configured to output concentration values for thesecompounds. The Model 933 utilizes two onboard microprocessors that provide concentration calculations, data processing,caliration, sophisticated self-diagnostics, and columnswitching control.

SpectraSensors SS 2100 Laser Based H2S Analyzershelp naturalgas processors, LNG plants, refineriesand chemical plants ensure trace hydrogen sulfide in mixed hydrocarbongases quickly and reliably with nohazardous waste or costly consumables MINIMAL MAINTENANCE Laser based technology is very reliablefor remote or hazardous installationsand requires very little maintenance.SpectraSensors analyzers work by directmeasurement. There are no chemical reactions to generate, no calibrationsneeded, and no results to interpret.

RELIABLE Spectra Sensors analyzers work by direct measurement. By itsnature, the TDL based H2S detectionmethod is not susceptible to agingeffects, making its factory calibration timeless constant. As a result,the factory calibration remainsstable over the life of the analyzer. Excellent measurement repeatability between instruments and as compared to lab instruments makes the SS2100 H2S analyzer the ideal measurement tool for even the most punishing of environments. The analyzers lower detection limit is 1 ppm in natural gas and 2 ppm in mixed hydrocarbons with operating ranges from 0-10 ppmv to percent level and repeatability as good as 500ppbv. EASE OF OPERATION Designed to be plug-and-play, the analyzers are remarkably easy to install; just connect power, the data link, and the measured gas line and the analyzer begins working. Once set up, measurements are performed in seconds. Analog and digital communications and alarm options are available as well as manual or automated H2S validation stream switching. Hydrogen Sulfi de - Sulphur Dioxide Analyzer: Product Specifications Utilizing pulsed fluorescence technology the Model 450i H2S and SO2 analyzer operates on the principle that H2S can be converted to SO2. As the SO2 molecules absorb ultraviolet (UV) light and become excited at one wavelength,the molecules then decay to a lower energy state emitting UV light at a different wavelength. Specifically, H2S -> SO2 SO2 +hv 1 -> SO2*-> SO2 +hv 2 The pulsing of the U.V. source lamp serves to increase the optical intensity whereby aGreaterU.V. energy throughput and lower detectable SO2 concentration are realized. Reflective band pass filters, as compared to commonly used transmission filters, are less subject to photochemical degradation and are more selective in wavelength isolation. This results in both increased detection specific city and long term stability. This state-of-the-art gas analyzer also offers features such as an Ethernet port as well as fl ash memory for increased data storage.Ethernet connectivity provides efficientremote access, allowing the user to download measurement information directly from the instrument without having to be on-site. You can easily program short cut-keys to allow you to jump directly to frequently accessed functions, menus or screens. The larger interface screen can display up to five lines of measurement information while primary screen remains visible.

Principle of Operation: Hydrogen Sulfide in Gaseous Fuels (Lead Acetate Reaction Rate Method). When hydrogen sulfide contacts the sensing tape a brown stain appears. electronics measure the rate of darkening over time and calculates the hydrogen sulfide concentration. A flow and pressure regulated filtered sample passes through a membrane humidifier and into the samplechamber. A window in the sample chamber allows thegas to come in contact with the sensing tape creatingconcentration dependent tain when hydrogen sulfide is present. In high concentration applications (over 20 ppm), there maybe a restricting aperture behind the window. Various sizes of apertures match different measurement ranges

Analyzer Diagram

H2S Analyzer Sample System Leave the sweep valve on the sample filter slightly open at all times. This will decrease the likelihood of contamination. If the analyzer requires cleaning on a regular basis, the sample point may have to be relocated or additional sample conditioning be required. Please consult Envent Engineering. During start-up or plant upset situations, the H2S analyzer may become contaminated with H2S scavenger solution.

This will cause the analyzer to read lower than the actual H2S concentration. This can be determined at calibration. The analyzer will read low and require incremental increases in the gain to maintain calibration. Please refer to factory calibration sheet for the default gain factor.

The flowmeter should be inspected for liquids and to ensure the float moves freely. The scavenger solution is water soluble and therefore is relatively easy to clean. Dis-assembly of the pressure regulator and solenoids in the field is not advised. Consult the factory if the regulator or solenoid appears contaminated. Remove the filter element from the filter housing and discard. Remove all sample system components and soak in cleaningsolution. Ensure valves are fully open when cleaning. 3-way valves should be cleaned with handle in all positions. Flush the sample components with fresh water. Rinse with isopropyl alcohol Blow dry with clean compressed air or fuel gas If Tygon tubing (flexible tubing connecting humidifier) appears discoloured, replace with new tubing Install new filter elements into filter housings . Re-assemble Stainless Steel Tubing to analyzer according to analyzer drawing (refer to the back of the manual) Once sample system has been re-assembled. Apply calibration gas to the analyzer. Adjust gain to indicate value from calibration certificate. Gains for streams should be +/- 2.00 from the factory calibration sheet or the last calibration. If the reading is not within range, then system may need further cleaning. Please consult factory

Introduction to Nuclear Radiation Detection: Nuclear radiation in any small doze is injurious to health. Nuclear radiation is invisible and has no smell or sound. It is not possible to detect all kinds of nuclear radiation with naked eyes or ears. There are several ways of detecting nuclear radiation. Nuclear radiation consists of several particles and has the capacity to ionize particles. These qualities are used in detecting these nuclear radiations. Methods for Nuclear Radiation Detection 1. Geiger Muller Counter: History: Hans Geiger developed a device (that would later be called the "Geiger counter") in 1908 together with Ernest Rutherford. This counter was only capable of detecting alpha particles. In 1928, Geiger and Walther Muller (a PhD student of Geiger) improved the counter so that it could detect more types of ionizing radiation. The current version of the "Geiger counter" is called the halogen counter. It was invented in 1947 by Sidney H. Liebson (Phys. Rev. 72, 602608 (1947)). It has superseded the earlier Geiger counter because of its much longer life. The devices also used a lower operating voltage. Description: Geiger counters are used to detect ionizing radiation (usually beta particles and gamma rays, but certain models can detect alpha particles). Here the radiation is passed through the Geiger Muller tube. The radiations have an ionizing effect. This property is used to detect radiation. In the Geiger Muller tube an avalanche and a pulse are created, it can be amplified and counted to identify the type of radiation.

GeigerMller tube (or GM tube)

GeigerMller tube in operation

GeigerMller tube output characteristics

 A GeigerMuller tube (or GM tube) is the sensing element of a Geiger counter instrument that can detect a single particle of ionizing radiation, and typically produce an audible click for each. A GeigerMuller tube consists of a tube filled with a low-pressure (~0.1 Atm) inert gas such as helium, neon or argon (usually neon), in some cases in a Penning mixture, and an organic vapor or a halogen gas. The tube contains electrodes, between which there is a potential difference of several hundred volts, but no current flowing. The walls of the tube are either entirely metal or have their inside surface coated with a conductor to form the cathode while the anode is a wire passing up the center of the tube. When ionizing radiation passes through the tube, some of the gas molecules are ionized, creating positively charged ions, and electrons. The strong electric field created by the tube's electrodes accelerates the ions towards the cathode and the electrons towards the anode. The ion pairs gain sufficient energy to ionize further gas molecules through collisions on the way, creating an avalanche of charged particles. This results in a short, intense pulse of current which passes (or cascades) from the negative electrode to the positive electrode and is measured or counted. Most detectors include an audio amplifier that produce an audible click on discharge. The number of pulses per second measures the intensity of the radiation field. Some Geiger counters display an exposure rate (e.g. mRh), but this does not relate easily to a dose rate as the instrument does not discriminate between radiation of different energies. Some Geiger counters can be used to detect gamma radiation, though sensitivity can be lower for high energy gamma radiation than with certain other types of detectors, because the density of the gas in the device is usually high, allowing most high energy gamma photons to pass through undetected (lower energy photons are easier to detect, and are better absorbed by the detector. Examples of this are the X-ray Pancake Geiger Tube). A better device for detecting gamma rays is a sodium iodidescintillation counter. Good alpha and beta scintillation counters also exist, but Geiger detectors are still

favored as general purpose alpha/beta/gamma portable contamination and dose rate instruments, due to their low cost and robustness. A variation of the Geiger tube is used to measure neutrons, where the gas used is boron trifluoride and a plastic moderator is used to slow the neutrons. This creates an alpha particle inside the detector and thus neutrons can be counted. Quenching The G.M. tube must produce a single pulse on entry of a single particle. It must not give any spurious pulses, and must recover quickly to the passive state. Unfortunately for these requirements, the positive argon ions that eventually strike the cathode become neutral argon atoms in an excited state by gaining electrons from the cathode. The excited atoms return to the ground state by emitting photons and these photons cause avalanches and hence spurious pulse discharge. Quenching of this process is thus important because a single particle entering the tube is counted by a single discharge, and so the tube is unable to re-set and detect another particle until the discharge has been stopped. Also, the tube is damaged by prolonged discharges. External quenching uses external electronics to remove the high voltage between the electrodes. Self-quenching or internal-quenching tubes stop the discharge without external assistance, by the addition of a small amount of a polyatomic organic vapor such as butane or ethanol; or alternatively a halogen such as bromine or chlorine. Applications: The Geiger-Mller counter has applications in the fields of nuclear physics, geophysics (mining), and medical therapy with isotopes and x-rays. Some of the proportional counters have many electrodes and are called multi-wire proportional counters or simply MWPCs. Radiation detectors have also been used extensively in nuclear physics, medicine, particle physics, astronomy, and in industry.

2. Scintillation Counter: History: The scintillation counter was invented in 1944 by Sir Samuel Curran[1][2] whilst he was working on the Manhattan Project at the University of California at Berkeley, and it is based on the earlier work of Antoine Henri Becquerel, who is generally credited with discovering radioactivity, whilst working on the phosphorescence of certain uraniumsalts (in 1896). Description: A scintillation counter measures ionizing radiation. The sensor, called a scintillator, consists of a transparent crystal, usually phosphor, plastic (usually containing anthracene), or organic liquid (see liquid scintillation counting) that fluoresces when struck by ionizing radiation. A sensitive photomultiplier tube (PMT) measures the light from the crystal. The PMT is attached to an electronic amplifier and other electronic equipment to count and possibly quantify the amplitude of the signals produced by the photomultiplier.

Fig: Scintillation counter including photomultiplier

Fig: Scintillation counter in operation When a charged particle strikes the scintillator, a flash of light is produced, which may or may not be in the visible region of the spectrum. Each charged particle produces a flash. If a flash is produced in a visible region, it can be observed through a microscope and counted - an impractical method. The association of a scintillator and photomultiplier with the counter circuits forms the basis of the scintillation counter apparatus. When a charged particle passes through the phosphor, some of the phosphor's atoms get excited and emit photons. The intensity of the light flash depends on the energy of the charged particles. Cesium iodide (CsI) in crystalline form is used as the scintillator for the detection of protons and alpha particles; sodium iodide (NaI) containing a small amount of thallium is used as a scintillator for the detection of gamma waves. The scintillation counter has a layer of phosphor cemented in one of the ends of the photomultiplier. Its' inner surface is coated with a photo-emitter with less work potential. This photoelectric emitter is called as photocathode and is connected to the negative terminal of a high tension battery.

 A number of electrodes called dynodes are arranged in the tube at increasing positive potential. When a charged particle strikes the phosphor, a photon is emitted. This photon strikes the photocathode in the photomultipier, releasing an electron. This electron accelerates towards the first dynode and hits it. Multiple secondary electrons are emitted, which accelerate towards the second dynode. More electrons are emitted and the chain continues, multiplying the effect of the first charged particle. By the time the electrons reach the last dynode, enough have been released to send a voltage pulse across the external resistors. This voltage pulse is amplified and recorded by the electronic counter. Applications: Scintillation counters can be used in a variety of applications. Medical imaging National and homeland security Border security Nuclear safety Several products have been introduced in the market utilising scintillation counters for detection of potentially dangerous gamma-emitting materials during transport. These include scintillation counters designed for freight terminals, border security, ports, weigh bridge applications, scrap metal yards and contamination monitoring of nuclear waste.

There are variants of scintillation counters mounted on pick-up trucks and helicopters for rapid response in case of a security situation due to dirty bombs or radioactive waste. Hand-held units are also commonly used.

Scintillation counter as a spectrometer Scintillators often convert a single photon of high energy radiation into high number of lower-energy photons, where the number of photons per megaelectronvolt of input energy is fairly constant.

 By measuring the intensity of the flash (the number of the photons produced by the x-ray or gamma photon) it is therefore possible to discern the original photon's energy. The spectrometer consists of a suitable scintillator crystal, a photomultiplier tube, and a circuit for measuring the height of the pulses produced by the photomultiplier. The pulses are counted and sorted by their height, producing a x-y plot of scintillator flash brightnessvs number of the flashes, which approximates the energy spectrum of the incident radiation, with some additional artifacts. A monochromatic gamma radiation produces a photo peak at its energy. The detector also shows response at the lower energies, caused by Compton scattering, two smaller escape peaks at energies 0.511 and 1.022 MeV below the photo peak for the creation of electron-positron pairs when one or both annihilation photons escape, and a backscatter peak. Higher energies can be measured when two or more photons strike the detector almost simultaneously (pile-up, within the time resolution of the data acquisition chain), appearing as sum peaks with energies up to the value of two or more photo peaks added.

IONIZATION CHAMBER The ionization chamber is the simplest of all gas-filled radiation detectors, and is used for the detection or measurement of ionizing radiation. Conventionally, the term "ionisation chamber" is used exclusively to describe those detectors which collect ion pairs from gases.

An ionization chamber is an instrument constructed to measure the number of ions within a medium (which we will consider to be gaseous, but can also be solid or liquid). It usually consists of a gas filled enclosure between two conducting electrodes (the anode and cathode). The electrodes may be in the form of

parallel plates (Parallel Plate Ionization Chambers: PPIC), or coaxial cylinders to form a convenient portable detector; in some cases one of the electrodes may be the wall of the vessel itself. When gas between the electrodes is ionized by any means, such as by alpha particles, beta particles, X-rays, or other radioactive emission, the ions and dissociated electrons move to the electrodes of the opposite polarity, thus creating an ionization current which may be measured by a galvanometeror electrometer. Each ion essentially deposits or removes a small electric charge to or from an electrode, such that the accumulated charge is proportional to the number of like-charged ions. A voltage potential that can have a wide range from a few volts to many kilovolts can be applied between the electrodes; depending on the application. The applied voltage allows the device to work continuously by mopping up electrons and preventing the device from becoming saturated. The current that originates is called a bias current, and prevents the device from reaching a point where no more ions can be collected. The essential components of the ionization chamber are its two collecting electrodes: the anode and cathode (the anode is positively charged with respect to the cathode). In most cases, but not all, the outer chamber wall serves as the cathode. The potential difference between the anode and cathode is often in the 100 to 500 volt range. The most appropriate voltage depends on a number of things such as the chamber size (the larger the chamber, the higher the required voltage).

The shape of the electrodes in an ionization chamber is more variable than those of a Geiger-Mueller detector or proportional counter. In general, the outer chamber wall (the cathode) is a cylinder or sphere while the anode is usually rod-shaped. Nevertheless, the anode might take other shapes, e.g., a cylinder or cone. In some cases, the two electrodes might even be flat parallel plates.

Another common type of ionization chamber is the well detector in which the outer chamber wall projects down inside a hollow tubular anode. This greatly increases the systems sensitivity because the sample can be positioned in the center of the chamber.

The presence of radiation causes charged particles to traverse the gas inside the ionization chamber. These charged particles might be alpha or beta particles from a radioactive sample (if they have sufficient energy to penetrate the detector wall). Alternatively, the charged particles might be electrons to which gamma rays or x-rays have transferred energy via the photoelectric effect, Compton scattering or pair production. Most of these gamma ray or x-ray interactions occur in the wall of the detector, but some also occur in the chamber fill gas. If the chamber wall is thin enough, these electrons might even originate in gamma ray or x-ray interactions outside the chamber.

The movement of the charged particles through the chamber ionizes the atoms or molecules of the gas, i.e., create ion pairs. For example, this ionization process might involve an electron being stripped away from a nitrogen molecule - the freed electron would be the negative member of the ion pair and the positively charged nitrogen molecule would be the positive member of the ion pair.

The electric field created by the potential difference between the anode and cathode causes the negative member (electron) of each ion pair to move to the anode while the positively charged gas atom or molecule is drawn to the cathode. The movement of the

ions to the collecting electrodes results in an electronic pulse. Since these pulses are usually too small to be detected, the most common approach is to measure the ion chambers current which is produced by many radiation interactions in the detector and is more easily measured than the individual puls.

Pulse-height analysis:
A common situation is the case when the signal consists of a series of pulses of essentially identical shape corresponding to a series of events. The pulses are related to each other by a random scaling factor so that significant information is contained in the height of the pulse, h, and how this quantity is distributed. The latter is described by the probability function p(h) defined so that the probability of occurrence of a pulse with height between h and h+dh is

In cases when the pulses are of microsecond or less duration the time for which the signal is approximately at h is extremely short so that special steps must be taken both to hold the height for analysis and to detect that the maximum has been reached. An arrangement to capture the peak height is based upon the sample and hold procedure. In principle the task could be accomplished by issuing the hold command the instant the maximum is reached. This approach is unsatisfactory since the timing requirements are too stringent. A simple addition to the circuit as shown in the diagram provides the solution. The main feature is the inclusion of the diode at the sample and hold input. During the rising portion of a signal at this input the current flow is forward and the diode conducts charging the capacitor, and the voltage across the latter follows the input. At the moment the peak voltage is passed the diode is back biased, so the peak voltage is held on the capacitor. The ancillary circuitry indicates some of the necessary interfacing to the ADC.

The control FF is set by the ADC end-of-conversion signal, EOC, opening the linear gate. The peak detector PD resets the control FF closing the gate, and signaling the ADC to start a measurement cycle. The gate remains closed until processing of the currently sampled pulse height is completed at which time an EOC is issued. The PD performs a role analogous to the internal trigger of an oscilloscope, indicating the occurrence of a signal at the input, as well as determining the time at which the peak is reached.

The principle of peak detection is illustrated in the accompanying figure. The input signal is differentiated. The derivative signal now crosses zero at the time the signal becomes maximum. The cross-over point is detected using a Schmitt trigger. This is designed so that the upper level and hysteresis value are identical so that the lower trigger level is precisely zero. The trigger fires when the input exceeds the upper trigger level H, returning when the input reaches zero. Peak time is then determined from the negative going edge of the Schmitt trigger output as indicated. Time mark generation by crossover detection is a generally important technique since the cross-over point is independent of the pulse height.

Once the conversion is completed the ADC contents are transferred to a memory address register, and the memory contents of the location at that address are incremented by one, indicating the occurrence of an event with height in the interval associated with the address. If a measurement is continued for a time T, during which period a total of NT events are processed, then the expected content of memory location n is

The data constitute a histogram approximating the probability density function if the quantizing voltage is sufficiently small so that the integrand may be approximated by a constant value p (nv0) over the integration interval v0. This type of digital measurement system is referred to as a multichannel pulse-height analyzer and has many applications. Three examples will be discussed. The first is connected to the technique of flow cytometry in which individual cells in suspension flow through a capillary. A fine beam of ultraviolet radiation is directed across the

diameter of the capillary so that a cell passes through it as it flows along. The ultraviolet light causes a specific molecular species such as DNA to fluoresce at a characteristic wavelength and the fluorescence is detected by a photo detector with the appropriate spectral response. The intensity of the fluorescence is determined by the DNA content of the cell and in turn determines the magnitude of the pulse from the photo detector induced by the cell passage through the UV beam. The photo detector output is coupled to a multichannel analyzer so that the distribution of DNA content in the cell population may be determined. The second example employs a device known as a Coulter counter to determine particle size. The counter consists of cell (as in dry cell - not biological cells of the prior example) containing an electrolyte. A pair of closely spaced electrodes with the electrolyte in the gap forms a resistor. Particles are suspended in the electrolyte and a flow is maintained. Diaphragms direct the particles individually to flow through the electrode gap. As the particle traverses the gap it displaces the electrolyte and increases the cell resistance. The amount of electrolyte displaced and hence the cell resistance is a function of the particle size. With the cell forming part of a divider chain connected to a voltage source the resistance change is converted into a pulse the height of which provides information regarding particle size. An important application is the size distribution of pigment in paints. The third example is the application for which the multichannel analyzer was originally developed, nuclear pulse spectrometry. An energy sensitive radiation detector responds to an interaction with a quantum or particle of radiation by issuing a pulse the height of which is proportional to the energy deposited in the sensitive material of the detector. The pulse height distribution acquired in a multichannel analyzer, usually referred to as a pulse height spectrum, provides information regarding the energy spectrum of the radiation.

Solid-state detector:

Solid-state detector, also called Semiconductor Radiation Detector, radiation detector in which a semiconductor material such as a silicon or germanium crystal constitutes the detecting medium. One such device consists of a p-n junction across which a pulse of current develops when a particle of ionizing radiation traverses it. In a different device, the absorption of ionizing radiation generates pairs of charge carriers (electrons and electron-deficient sites called holes) in a block of semi conducting material; the migration

of these carriers under the influence of a voltage maintained between the opposite faces of the block constitutes a pulse of current. The pulses created in this way are amplified, recorded, and analyzed to determine the energy, number, or identity of the incidentcharged particles. The sensitivity of these detectors is increased by operating them at low temperaturescommonly that of liquid nitrogen 164 C (263 F) which suppresses the random formation of charge carriers by thermal vibration. GaAs, CdZnTe and other high density solid state materials are good candidates for the detection of X-rays in the typical energies for Radiography (1-100 keV). In fact high Z allows for high detection efficiency and, as a consequence, for dose reduction to the patient. Their properties are affected by heavy trapping for charge carriers: stronger and more uniform electric field could improve collection efficiency and spectroscopic characteristics. Our research aims towards development of new techniques for contact deposition and of new structures and geometries which could improve charge collection efficiency (cce) and energy resolution. Measurements are also performed in order to study timing characteristics of such materials.

Naturally Occurring Radiation

Naturally occurring radiation can be found all around us. Radiation can be found in soils, in our air and water, and in us. Because it occurs in our natural environment, we encounter it every day through the food we eat, the water we drink, and the air we breathe. It is also in building materials and items we commonly use. There are three groupings of naturally occurring radiation, mostly based on where the radiation comes from. First there is the radiation in the soils and rocks, called primordial or terrestrial. Then there is radiation that comes from space, called cosmic or cosmogenic. The third is human-made, something created by humans that wouldnt exist otherwise or something that contains more radiation in it than normal (enhanced) because humans have done something to it.

Industrial Uses There are many industrial uses of radioactive materials, including material density evaluation, product sterilization, quality control, static elimination, and electricity generation. The radiation sources used for these processes include radiation-producing machines and sealed-source radioactive materials, to name two. In this section, we are going to describe a few of the uses that routinely improve our lives. Advantages and Disadvantages of Radioactive Sources In the United States, millions of radioactive sources are in use by tens of thousands of authorized users (licensees). The amount of radioactive material authorized for these licenses ranges from one-millionth of a curie, which is typical for the sources used in gauges, to millions of curries such as those used in large irradiators. Advantages While there are some specific advantages to using sealed sources that are distinct to various industries, the major advantages are essentially the same across all the industries. Sealed sources have the following characteristics that make their use advantageous for industry:

Robust, sources are amenable to a variety of environments Reliable while the detection of the emitted radiation can be sophisticated, the energy source is simple and can not fail Portable energy source not requiring other sources of energy (e.g., electricity) for operation Range of energies Easily transportable Interact with other media in well defined manner that facilitates various measurements Do not require contact with other materials or media for use Devices are typically easy to use and do not require sophisticated operator training Commercially available from a large number of vendors in a variety of forms and energies Mature technology

Disadvantages There are a number of disadvantages to the use of radioactive sealed sources that are common to all industries. These include:

Need for precautions to prevent exposure of individuals to harmful radiation Energy source is always on, thus requiring significant attention to storage Loss of the source can create an environmental and health hazard Spent sources require appropriate disposal

There are a number of disadvantages to the use of radioactive sealed sources that are common to all industries. These include:

Need for precautions to prevent exposure of individuals to harmful radiation Energy source is always on, thus requiring significant attention to storage Loss of the source can create an environmental and health hazard Spent sources require appropriate disposal

Common Industrial Devices Portable Moisture/Density Devices A type of industrial gauges that are small and portable. These devices contain the sources, detectors and electronic equipment necessary for the measurement. The source is physically small in size, typically a few cm long by a few cm in diameter, and may be located either completely within the device or at the end of a rod/handle assembly. The small size of the device makes it susceptible to loss of control or theft. Industrial Fixed Gauges Devicesare of various shapes and sizes. These devices are generally designed for many years of operation with little or no special maintenance. Industrial gauges are used for process control; for measurement of flow, volume, density, or material presence; and may be placed in locations unsuitable for continuous human presence (e.g.: in a blast furnace). Consequently, they often accumulate layers of dirt, grime, grease, oil and other material that may cover any warning labels that may have been present. Depending upon the specific application, industrial gauges may contain relatively small quantities of radioactive material, or may contain sources with activities approaching 1 TBq. The devices generally are not large, but may be located some distance from the radiation detector, which may have electrical or electronic components located within the detector. A facility may have a large number of these gauges. The locations of such devices or sources within a facility may not be recognized, since the devices may be connected to process control equipment. This lack of recognition may result in a loss of control if the facility decides to modernize or terminate operations. Industrial Radiography Cameras These devicesare generally small in terms of physical size, although the devices are usually heavy due to the shielding contained in them. The sources themselves are very small, less than 1 cm in diameter, and only a few cm long, and are attached to specially designed cables for their proper operation. The use of radiography sources and devices are very common, and their portability may make them susceptible to theft or loss. The small size of the source allows for unauthorized removal by an individual, and such a source may be placed into a pocket of a garment. Industrial radiography may also be performed in fixed installations, either using the same small portable devices, or using larger machines. Well Logging Devices These devices are generally found in areas where exploration for minerals is occurring, such as coal, oil, natural gas. The sources are usually contained in long (12 m, typically) but thin (<10 cm in diameter) devices that also contain detectors and various electronic components. The actual size of the sources inside the devices is generally small. 25 The

devices are heavy, due to the ruggedness needed for the environments in which they are to be used. Overview of Common Industrial Uses of Sealed Radioactive Sources EPA has begun the process of evaluating some of the most common applications of sources to identify the potential for developing alternative technologies. The table below provides an overview of the major industrial applications for radioactive materials. (Information sources: Uranium Information Center (UIC, 2001); US Nuclear Regulatory Commission (NRC, 2002).) Industry: Products/Services Manufacturing:

Use Measure:

Types of Sources Gamma emitters such as:

numerous

thickness of metal components thickness of coatings moisture content in manufactured products

barium-133 cobalt-60 cesium-134 cesium-137 antimony-124 selenium-75 strontium-90 thulium-170 Gamma emitters neutron sources (for level measurement)

Chemical Processing:

Measure process characteristics, such as:

various density thickness of coatings specific gravity level

Measure equipment parameters such as:

pipe thickness corrosion wear Gamma emitters; neutron sources such as:

Construction:

Measure:

buildings, geophysical structures

moisture content location of reinforcing bar (rebar) density gauges

Americium/Beryllium plutonium/beryllium californium-252

Mineral Processing:

Gamma emitters, such as:

spectroscopy

measuring mineral levels in process streams Measure:

americium-241 cobalt-57 cesium-137

Coastal Engineering:

Gamma emitters, such as:

measuring environmental parameters

levels of sediments in rivers and estuaries mobilization of sediment

americium-241 cobalt-57 cesium-137

Non Destructive Examination:

Measure:

radiography

weld and weld overlays castings forgings valves and components machined parts pressure vessels structural steel aircraft structures column scanning level measurement

cobalt-60 cesium-137 iridium-192

Oil Refining:

refinery products

Gamma emitters (column scanning); neutron sources (level measurement) especially americium-241/berylliumGamma sources such as cesium137 with americium-241 (for ash content)

Coal Fired Boilers:

Measure:

electricity generation

ash and moisture content of coal

Drilling / Borehole Logging:

Measure:

geophysical investigations

hydrogen content

Gamma emitters, especially Cobalt-60, and neutron sources americium-241/beryllium

Agriculture:

Measure:

Neutron sources such as:

various crops

soil moisture

americium/beryllium plutonium/berylium

measurements Hydrology:

californium-252

Measure:

neutron sources such as:

environmental assessments

soil moisture

americium/Berylium plutonium/Berylium californium-252

Consumer Products:

smoke detectors

Produce an ionization current that is affected by the presence of smoke Measure:

Alpha emitter typically americium-241

Materials Processing:

Gamma emitters, such as:

blown film cast film and sheet rubber vinyl coatings & laminations nonwovens textiles composites paper plastic pipe film thickness electroplating

thickness or americium-241 weight basis Beta emitters such as: weight consistency praseodymium-147 moisture content prypton-85 strontium-90

Various:

remote weather stations weather balloons navigation beacons and buoys

Power sources for applications requiring small amounts of portable energy

Recording Industry:

dust and static control

Product Labeling:

dust and static control