Process Instrumentation 3A (PINA301)

TOPIC 1 NOTES - ANALYSERS

N.B Prescribed/Recommended Books
Instrument Engineers Handbook (Vol. 1: Process Measurement & Analysis
Instrument Engineers Handbook (Vol. 2): Process Control and Optimization
Process Industrial Control Handbook
PINA NOTES
PAST PAPERS

Mthabiseni Mbokazi
 ANALYSERS
1.1 ANALYSER APPLICATION AND SELECTION (page 1185 Vol 1)
➢ Purpose of analytical instrumentation – very difficult measurement which cannot be measured using common
techniques. Alternative methods are used to measure these measurements.
Example – pH is difficult to measure because of many variables surrounding the measured variable these include
Temperature, Flow Rate, Fluctuations & Pressure, these all affect the pH measurement.
➢ Analytical Instrumentation is born out of the lab, for Example a liquid in a small container, to measure the pH on
the liquid, analytical measurement has to be applied to the liquid which is a system of processes in order to
extract the measured variable which is pH.
➢ Moving out of the lab to the Industrial Analyser is more complex because there is no controlled lab environment.
➢ Devices like pumps, filters and transducers and a display to convey the information to the user are available.
➢ This forms the part of the analytical devices.
➢ These devices (Analytical Devices) are expensive, intricate, and required sufficient training to operate and
maintain in plant.
➢ Analytical devices are least understood because many of the measured variables that are often diverse in nature
like pH, Conductivity, Opacity, Turbidity, measurement of gases like Chlorine, Carban Dioxide and Oxygen.
➢ They are also least understood because of the processing which is to isolate that specific type of measured
variable becomes costly to run a device with all the intricate parts, there will be severe cost implications for
analysing devices.
Analytical instrumentation devices are least understood due to:

• Lack of understanding of measurement principles

• Nature of process variable involved.
• Chemical makeup of target,
• Sample systems – this includes pipes, pumps with a degree of sophistication.

➢ Measurement strategies also cause a problem if poorly understood.

➢ These have to be remembered when selecting an analyser for an analyte or target which is the common
one like pH, Conductivity, Turbidity (how clean or dirty the water), these measurements are predominantly
for water.
➢ pH, Conductivity, Turbidity and Chlorine are all important quantities to indicate the water quality.
➢ Processing facilities like water treatment plants all require some level of indication of how good the water
quality is.
➢ If these are not measured or measured incorrectly would degrade the end product quality control.
➢ For environmental purposes it is important to measure gases like CO2, NOx, O2 to have measure and
knowledge.
USES OF ANALYSERS
➢ Raw Material Monitoring – When there are gases used in a process the number of gases in a specific pipeline has
to be measured, for example if the gas is Oxygen there should be an Oxygen Analyser in that pipeline.
➢ Process Control – Important for analysing devices for example in Distillation Columns, through the distillation
process or heating up a liquid, there are by-products and those by-products have to be measured at the output.
If it is alcohol Distillation Column, the product is alcohol, the percentage concentration coming out of the
distillation column has to be measured, this can be done using Alcohol Based Analyser.
➢ Process Troubleshooting - If there is a problem with process using a gas or liquid an analyser can be used in that
tank.
➢ Yield Improvement – In the process of creating a product out of a distillation column, in order to get a better
yield or reaction going inside the distillation column the temperature and the pressure inside the distillation
column has to be controlled, there will be analyser devices at the output measuring the output.

➢ Inventory Measurements - Stock of the inventory as some gases and liquids are expensive there must be a system
or measurement taking place to have feedback to the operator telling them to cut back if too much inventory is
being used, an analyser can be used to indicate if too much inventory is used.
➢ Product Quality – Analysers are used at the end of operation or manufacturing process for example in the paper
industry there is moisture analysers to pick up moisture of the paper product.
➢ Waste Disposal and Monitoring - Processes have waste products in the form of liquid, gases which are vented
out. There must be analysers to monitor those waste products (gases & liquids) as they can cause harm to the
environment. The gases and liquids are emitted from the process and are often by-products.

❖ Pollutants - Substances in the air/water that cause harm to humans and the environment. Can be emitted directly
from the process.

1.2 COMMON TERMS AND DEFINITIONS

Quantitative Measurement: measures the exact amount of material in a sample. Chemical makeup of sample is
unknown, for example pH, Conductivity, Turbidity, Opacity.

Qualitative Measurement: Exact amount of substance present in the solution is measured. Measures the chemical
makeup and its relative quantity. Output may be Organic particles, Gases, Salt, or Sugars in H2O. for example, gas
chromatography – water is boiled, the analyser picks up all the constituents present in H2O and gives measurement
of what water is made up of.
Qualitative is more advanced and cost more.
Analyte: Component of interest (COI), target sample of the process, e.g., Percentage Oxygen, pH, Conductivity.
Cross Sensitivity: measurement is affected by more than one variable, for example pH which is a cross sensitive with
temperature variations. If there is analytical device in plant measuring liquid or gas that is varying in Temperature,
that is going to affect the pH measurement.
Invasive Measurement: When sensor probe affects the normal process flow. If a liquid is extracted from a pipeline,
then taken to the analyser device for analysis, there will be some measure of intrusion into the process and that is
Invasive Measurement.

Continuous Sampling

Non-Invasive Measurement: Where other techniques are used such as nuclear methods, infrared, light base
(spectrum of light) to extract the component of interest based on absorption levels. There is no contact between the
analyser and the tank or pipeline.

1.3 SAMPLING METHODS

If there is pipeline and measurement have to be taken, the sampling method would lead to having Invasive
Measurement like drilling a hole and creating a tap off point and sampling line.
➢ Refers to invasive like drilling a hole and creating a sampling point.
➢ Poorly designed sampling can compromise the sampling.

Tap-Off Point
Sampling Systems Can Be Classified into Two:
Continuous Sampling
▪ Like drilling a hole, the valve continuously extract the component of interest as the flow rate is changing.
▪ The liquid will be continuously sampled by continuously opening the valve.
▪ The liquid flowing will get sampled.

▪ The analytical transmitter will continuously measure the liquid before it goes back to the pipeline. The COI is
continuously measured as the flow rate is changing.

Grab & Hold (Discrete Sampling)

➢ This employs a series of valves. These valves are controlled by machinery.
➢ The machinery closes the valves as soon as the sample are taken in.
➢ The sample is cleaned for measurement on the AT.
➢ Then the measurement is displayed, and the liquid goes back to the pipeline.
Advantage - Product is not wasted.

Grab and Hold

1.4 THREE GENERAL CLASSIFICATIONS OF SAMPLING METHODS

At-line method - manual method of sample retrieval and measurement
➢ If the sample has to be taken or analyte or COI, the operator will manually open the valve/tap to fill the beaker
with the sample then take it to the lab for assessment and manually analyse it.

Sample on the beaker taken to the lab for assessment.

-
Advantage - Gives accurate readings.
Disadvantage - The sample can be contaminated.
- Temperature affects reading.
- Has a large lag time.
On – line – Uses sample pipes to divert flow to the analyser device.
- Sample pipes may change the nature of the process or sample properties.
- Large time lag if the pipes are too long.
- Filtering used is coalescing and Scrubbing.

A
Prevents damage to the AT

➢ There is a tap on point, filter system.

➢ If the process is not expensive it is the drained, otherwise it is returned back to the process pipeline.
➢ The filter prevents any analytical damage to the transmitter.
➢ If there is a liquid on the pipeline and pH has to be measured the filter will filter out sediments/particles in the
liquid so that the analytical transmitter is not destroyed.
➢ Sample pipes change nature of the process, the temperature from point A to B will be different.
➢ Filter removes particles which is coalescing and scrubbing.
➢ This method is considered if there are many impurities in the pipeline that have to be filtered.

Factors That Can Affect the Lag Time of The COI On-Line
➢ Sample Line Length and Diameter: The length and diameter of the sample lines in industrial analyser systems
play a crucial role in lag time. Longer and narrower sample lines result in higher pressure drops and longer
transport times for the sample to reach the analyser. Designing sample lines with appropriate lengths and
diameters can help minimize lag time.
➢ Sample Conditioning Equipment: The efficiency and performance of sample conditioning equipment, such as
filters, heaters, coolers, and pressure regulators, impact lag time. Properly designed and maintained conditioning
equipment ensures that the sample is prepared and delivered to the analyser without delays caused by
temperature variations, contaminants, or pressure fluctuations.
➢ Process Dynamics: Processes with fast response times may result in shorter lag times, while slower processes
may introduce delays in detecting changes. Placing the sample point closer to where the COI concentration or
parameter changes occur can minimize lag time by reducing the distance the sample needs to travel.
Alternate scheme for On-Line - changing the flow rate speed.

In-line method (in-situ): probe is directly inserted into the pipeline.

Advantages - Changes are rapidly detected.
- Has least lag time
Disadvantage – impurities in the pipeline can damage the transducer module.

1.5 PARTS OF AN ANALYZER SYSTEM

➢ Has process, Extract, Conditioning, Measure and Display.
I. Process – measure the component of interest, it could be quantitative or qualitative.
II. Extraction – through a sampling pipeline and can be a series of valve arrangements and pumps.
III. Conditioning – there are filters, temperature, pressure, speed, and the phase manipulation.
IV. Measure/Analysis – measurement or analysis of COI, this is where there is a transducer. The measurement is
converted to an electronic signal. After this the sample can be returned to the pipeline or it can be sent top the
drain.
V. Display – the measurement/measured variable is displayed or printed out.

Sample Extraction – two types Continuous and Discrete. The purpose of having extraction system is to reach to a
process to obtain a representational sample.

− Transport packet of sample to safe location without loss or change in chemical make up the analyte.

− Calibrate to a known standard (Calibration can be done in SI-TU).

- Display results, output goes to the PCS to alert the operator.
➢ For Continuous measurement this done all the time for Discrete measurement it is done periodically
➢ The system can switch from one stream to another this is called Multi-Stream Switching.
 ➢ For A valve 1 will open, then close
➢ For B valve 2 will open, then close

➢ Pipelines A and B when there is a transfer of liquid or gas from one point to another the sample will change in
term of pressure and temperature. If there is a hot liquid in A, there should be heating jackets on the sampling
pipelines to prevent heat loss, so it will be at the same temperature and pressure when it reaches AT
➢ The sample is prepared for a specific isolation of target chemical, when dealing with specific chemical they have
to be filters.
➢ Calibration when dealing with discrete or continuous analyser devices have to be calibrated periodically. All
measurement devices have to be calibrated to give the best readings.
➢ Display and report results, the analyser devices usually have an output the output will go the PCS, the PCS will
use the information to alert the operator on the screen or give back information back to the process to control
things like valve, downstream and upstream.

1.6 CONTINUOUS VERSUS DISCRETE SAMPLING METHODS

• Reach into process to obtain a representational sample, small quantity.
• Switch from one stream to another (multi-stream switching).
• Transport packet of sample to a safe location without loss or change in chemical makeup of analyte.

• Transfer to point of return or rejection.

• Prepare sample for specific isolation of target chemical.

• Calibrate to a known standard.
• Display and report results.

1.7 SAMPLE EXTRACTION AND CONDITIONING (CLEANING/REMOVAL OF IMPURITIES)

➢ Filtering – There are micron filters, paper filters, mashed filters used to remove impurities, so that it will not
degrade the transducer element. Filtration has to be maintained timelessly and will require some maintenance.
➢ Centrifuging – uses the effects of the centrifuging action, centrifuging example is filling bucket with water and
swing around, the liquid will not splash out the faster you swing the more the liquid will stay in the bucket due to
the forces of centrifugal. This is applied in filters heavier particles like dust or dirt, or organic matter are collected
by these centrifugal forces. As the liquid gets in the centrifugal component it spins around and collects all the
heavier particles then they are disposed.
➢ Washing (Scrubbing) – if there is a gas wanted as a COI, it has to go through a transducer device which requires
it to be in a different phase/form. Washing/Scrubbing a liquid passing through a gas, the gas is absorbed by the
liquid, then the liquid with the absorbed gas is sent to the analyser devices.
➢ Bubble Removal – bubbles cause problems if the liquid is moving at high speeds, the bubble will affect the actual
reading and it will start to fluctuate. This can be avoided by using On-Line methods, the liquid can be slowed
down by changing its speed or there can be air removal systems/air trapping systems.
➢ Ultrasonic Vibration – can be used to move any particles. Removes particles or solid matter that could affect the
reading. Ultrasonic vibration uses high-frequency sound waves to agitate and dislodge particles or contaminants
from surfaces. It is effective for cleaning components or removing stubborn deposits in analyser systems
➢ Condensing (Air Cooling, Water Cooling, Refrigeration) – it is used to cool main process variable to sufficient
levels. If it is a gas Air cooling is used.
➢ Pressure Reduction/Flow Control – can be done by using regulators or orifice plates to reduce pressure. Pressure
and Temperature work hand in hand, to manipulate the phase of liquid or gas. Orifice plate or regulator can be
used.
➢ Component Isolation (Column Separation, Membranes, Coalescing) - This is used to remove impurities by
coalescing which is a process where there are small particles collecting into bigger particles. If there is Air coming
to the coalescing membrane filter, the air has impurities which can be oil. The oil is collected on the side.

Filter

- Pressure at PT-1 will go up, at PT-2 it will be low.

Isokinetic Sampling – Isokinetic sampling ensures that the sample is collected at the same velocity as the
surrounding medium, minimizing velocity related errors
- Higher mass components will only reach analyser if velocity of the sample is higher.
- Used for two phase samples, e.g., liquid/gas.
Non-Isokinetic – refers to a sampling method where the sample is not collected at a constant velocity or flow rate
relative to the surrounding environment.
- May introduce biases or inaccuracies in analytical measurements, especially in situations where the sample
velocity varies or is not controlled
Phase Preservation - Phase preservation refers to maintaining the integrity and stability of the phase (liquid or
gas) of the sample throughout the measurement process.
❖ This is crucial in analytical measurements because changes in the sample's phase can alter its composition or
properties, leading to inaccurate results.
❖ Techniques such as proper sample handling, temperature control, and avoiding phase transitions (e.g.,
evaporation, condensation) are used to preserve the phase of the sample during analysis.
➢ Each gas or a liquid has its own Critical Point
➢ For example, if there is an analyser measuring oxygen that oxygen will have a specific Bubble Point and a specific
Dew Point (turn into gas or liquid).
➢ If the analyser is designed to measure oxygen in gaseous phase, then it has to be at a certain pressure region and
certain temperature region.
➢ If it goes beyond the critical point, it can create problems for measurement.
➢ Phase preservation is important when dealing analytical devices.

SAMPLE EXTRACTION AND CONDITIONING

Average Of Multiple Samples – Used to find representational measurement of varying concentration gradient
in a large pipelines or smokestacks.
➢ Has multiple AT, because of different concentrations of gas in a pipe/tank
➢ By placing 2 or more measuring analysers it gives a representation of the system.
➢ Use multiple sampling points
➢ Sample turbulent stream flow, liquid mixed & give an average representation

Shape Of Equipment

➢ Shape of process equipment causes measurement problems depending on the vessel.

➢ Depending on the Distillation Column if it is large pressure, temperature at different points need to be obtained.
➢ A reading on the output has to be employed, using an accumulator tank, analyser on the output of the tank.
 Accumulator Tank

QUENCHING REACTIONS
Liquid in the pipeline undergoes reaction the state is changing; temperature and pressure are also changing.
- Before taking it to the analyser there must be some mechanism in between to stop that change and to present the
analyser with a stable representation.

A
B

1. Cooling Water Jackets

▪ Cooling water jackets can be used around the sampling tube/probe.
▪ As the liquid goes from point A to point B the liquid will cool down, temperature drops at a suitable level to
affect the chemical nature of the liquid and it stops the reaction.
▪ The analyser can then take a safe measurement.
▪ Use of quench type probe – cooling water jacket.

2. Expansion Cooling
▪ Nozzle/orifice plates can be employed which causes pressure to drop and this affects the temperature.
▪ Combination of cooling water jackets and Expansion cooling can be used.
3. Dilution
▪ A known liquid or gas is injected into the stream affecting the reaction rate.
▪ Dilution can cause calibration error because a foreign/unknown liquid or gas is introduced into the process line.
Scrubbing Systems – devices used to remove some gases or particulates from a gas exhaust stream for the
purpose of measurement.
❖ Wet Scrubbing – water is used to run through the exhausts gases to obtain gas concentration sample.
❖ Dry Scrubbing – uses gas absorbent material to remove the target gas from the exhausts steam.

Contaminant Removal – rejection of unwanted solid particles from the sample.

o Uses probes fitted with filters.
o Slipstream filters to change speed/velocity of liquid.
o Sparges & packed towers – tower filter with coal to absorb any unwanted gases before the analyser.
o Water washing probes.
o Internal separation probes
o Homogenizers

Coalescing Filter – removal of liquid. (Page 1217 Vol 1)

Working Principle of Coalescing Filter Click Here

▪ The mixture of Gas and with Oil droplets enters the through the Inlet.
▪ As the mixture passes through the Inner Foam Sleeve, the tiny oil droplets start to coalesce, or come
together, forming larger droplets.
▪ The mixture then moves through a Filtering Media which collects the larger oil droplets while allowing the
air to pass through.
▪ The mixture, now with fewer Oil droplets, passes through an Outer Foam Sleeve which coalesces any
remaining small Oil droplets into larger ones.
▪ The larger Oil droplets, now heavy enough to be separated from the Gas due to gravity, fall to the bottom
of the filter.
▪ These collected Oil droplets are then drained out through a Liquid Drain.
▪ Then a good clean filtered gas will go out
Sparger Tower (page 1217 Vol 1)

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enters the scrubbing
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This increases contact
the liquid–gas surfacesurface
contact area and
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o oAt theAtsame time, time,
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the bubbles also increase
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the tendency and liquid
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carryover,
and and therefore
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therefore flow velocities
sample flow should be should
velocities kept low.
be kept low.

Packed Tower Scrubber (page 1217 Vol 1)

➢ Packed towers can also be used as scrubbers.

• The gas sample bubbles up through a nonreactive packing of

beads that are wetted by a liquid solution.

• Foaming and liquid carryover are problems in packed towers, as in

a sparger

Slipstream Plus Coalescing Filter (Page 1219 Vol 1)

− Used in high flow rate and continuous sampling systems.

− Used for bubble removal from a liquid
Working Principle of Slipstream Plus Coalescing Filter
o Inlet has a higher flow rate from high pressure (inlet), bypass
to High Flowrate
o Gas/liquid goes at a reduced velocity to the coalescing filter
which removes all the particles and is changed from liquid to
gas form.
o Pressure reducing valve collects the gas and send it to the
analyser.
Bypass Filter with Rotating Mechanism (Self Cleaning) (page 1220 Vol 1)
- Used to Remove dust.

Working Principle of Slipstream Plus Coalescing Filter

o Liquid goes into the centrifuging body which is spinning.
o Because of the centrifuging action, the heavier particles/impurities
collect on the outside.
o The filter element collects it, clean the liquid or gas and send it out
to the analyser devices.

Sample Transfer Lines

➢ Very important consideration as it affects both transportation delay and velocity of sample.
➢ Process pipe is thicker than sampling lines.
➢ Depend on the diameter of sampling line, affect time taken to the analyser.
➢ Sampling line is affected by length, longer sampling lines have more delay of transportation and vice versa.
➢ For systems that require feedback control, this is detrimental and for systems requiring the same phase.
➢ Temperature and Viscosity - high temperature, Low viscosity. Heating jackets are needed on the sampling line.

A
B

FOR FASTER RESPONSE CONSIDER

• Supply Pressure - at point A Consider supply pressure is enough pressure to push the liquid or gas through.
• Sample return point - There will be sample return point at B.
• Actual Distance Between Take Off Point and Analyzer Electronics - Distance from A to C, will affect the
lag time and there will be no good feedback.
• Sampling line Diameter - It cannot be too thick, and it is the same time, it cannot be too thin as it will
affect velocity.
• Delays Caused by Filters, Rotameters, And Pipe Bands.
• Sample Transport Properties (Temperature, Viscosity) - The higher the temperature the lower the
viscosity. Higher viscosity liquid such as oil will be affected greatly by the temperature. Heating jackets
should be employed to prevent any malfunction or any pully transmitted points between the sampling
lines.

Liquid Sampling System (page 1222 Vol 1)

▪ Has shut off valves.
▪ Self-cleaning filter (Ultrasonic Filter)

PI – Pressure Indicator
TI – Temperature Indicator
Working Principle of Liquid Sampling System
➢ Sample comes in, goes to the Shut-Off Valves.
➢ To the Self-Draining Filters (ultrasonic Filter)
➢ It goes to the Sample Cooler (cooling can be required because the sample may undergo a chemical reaction) –
cooling water comes in/have to be put in.
➢ Then the sample goes to the Pressure Regulator to ensure the pressure is fine after the sample cooling.
➢ It goes to the Coalescing Device which removes the impurities.
➢ Goes past the Pressure Indicator, Temperature Indicator, Flow Indicator then to the analyser.
➢ There is Sample Calibration Point – usually used to take a manual sample coming into the system. The sample
can be taken to the lab.
➢ The sample is returned to the Drain or Set Point.
➢ There Are Flow Indicators, Check Valves to ensure that there are no blockages or leakages in the system.
❖ N.B: if the Shut-Off Valves, Pressure Regulator are open the system has a continuous flow which is continuous
sampling.
DISCRETE SAMPLING VERSUS CONTINUOUS SAMPLING.
Discrete Sampling
▪ Sample measured at specific intervals.
▪ Allows for automated manner.
▪ Allows for less wastage.
▪ Allows for automated system clean-up especially when dealing with multi-stream switching (if there are two or
more streams to measure), has to be cleaned up before taking a new measurement.
▪ Allows for high velocity transport.
▪ Can be designed for automated calibration.
▪ Provides real-time validation – makes sure the device is working according to the specification.
Discrete Sampling System
▪ Pipeline has a gas to be measured.
▪ This has sampling system with a sample and hold arrangement.
▪ There is a piston or gas cylinder.
Extracted Volume Sample

Air Piston
F

Working Principle of Discrete Sampling System

➢ Air is sent to valve A, when A opens up, it allows Air Piston to Retract.
➢ The extracted sample moves to the position of Carrier Gas.
➢ Carrier Gas is a non-volatile has (does not react with the gas in the pipeline) it pushes the extracted sample to
the analyser.
➢ The Extracted gas sample goes to the analyser and measured and gives out reading/results.
➢ After some time, Valve A closes, Valve B opens, the analyser sends a signal to Valve B to Extend the Air Piston
and pushes the extracted sample back to the pipeline.
➢ Another sample is extracted, Valve B closes, and Valve A opens to retract the Air Piston and a new sample comes
in and goes to the analyser.
Real-Time Automatic Calibration (IN-SITU Example)
➢ The analyser can retract the gas to the reference sample instead of picking up the Extracted Sample Volume, it
goes to Valve C.
➢ The Calibration Sample /Reference Sample is collected, whatever gas is at D is Vented Out.
➢ The calibrated sample moves up by opening Valve B to extend the Air Piston
➢ The reference sample goes F then it is sent out to the analyser for calibration.
1.8 CALIBRATION AND VALIDATION FOR ANALYZERS
Methods For Calibration

External Standards
▪ Use of known reference sample in place of the process analyte.
▪ Standard reference must be known and from a reliable source.
▪ Several measurements must be taken to ensure stability and repeatability.
▪ Calibration tests must be carried out under similar operating conditions if possible.

Internal Standards
▪ Introduce known amount of reference into unknown process sample. (Ratio of sample to reference is critical).
▪ Concentration of target analyte is calculated from the ratio of the responses of the reference and target
components.
Disadvantages/Why it is used for Internal Standards
▪ Real time measurement not substantially affected.
▪ System not disturbed by switching the reference standard samples.
Control Sample
▪ Same method as the internal standard except we inject reference at specified times.
▪ Used when the system cannot be stabilized easily.
▪ Must be used with careful consideration due to cross contamination and degradation of precision of both
samples.
Secondary Standard
▪ Used laboratory analysis of the process sample and compare it to the analyser measurement.
▪ Used when there is no reference standard available.
▪ We calibrate analyser to match the laboratory results.
▪ May require several measurements to be taken.
Auto Calibration
▪ A standard sample is bottled and used periodically by the analyser to calibrate at every interval.
▪ Complex valve arrangement.
▪ May use a considerable amount of standard sample.
❖ Validation is Proof of performance in real time. Verify the stability of the analytical system for a fixed period.
Instrument drift is undesirable and affects accuracy.

1.9 ANALYZER MEASURING PRINCIPLES

Chromatography.
Electromagnetic energy (UV Vis, IR and NIR).
Electrochemical.
Mass spectrometry
❖ Needed because of the diverse of nature of sample/measured variables.
CHROMATOGRAPHY
▪ Used to separate the component of interest in a sample that contain a mixture of volatile components.
▪ Measure chemical makeup of sample.
▪ Most common apart from pH
▪ It is a Qualitative Measurement – measures the actual make-up of the substance, tells chemical make-up of
sample concentration.
Example of Chromatography
- Dip paper in solvent (Paraffin)
- Put colours of ink (red, blue, and orange) in the sun, put in the sun.
- Dots will expand into individual colours over a period of time called Elution Time.
- After that the make-up of the inks will be seen.
GAS CHROMATOGRAPHY
Oven temp. varied (50 – 225 degrees Celsius)

Consist Of the Following

▪ Supply carrier gas, which regulates pressure.
▪ Sample in introduction device to inject a fixed volume of sample into the carrier gas stream.
▪ Column containing the stationary phase and a detector.
Working principle of Gas Chromatography - Click Here
➢ Sample comes in the Injection Device (it will go through sample extraction, conditioning, and coalescing)
➢ Carrier gas also comes in (Helium, Nitrogen, Hydrogen) these do not react with the sample gas.
➢ The sample goes to the Mobile Phase, it passes it into the Column (Which is a piece of coiled tube) it is coiled up
to create large surface area.
➢ The gas stays in the Column, which is the Stationary Phase.
➢ Heat is applied on the Column (stainless steel is used for large surface area)
➢ Whatever gases the sample is made up of will move out of the Column, depending on the molecular constituents
present.
➢ All gases are detected by the Detector, the detector converts the detected gas (measured signal) and covert into
an electronic signal then into a Chromatograph (which shows all the gases).
➢ The gases are then vented out to the atmosphere as waste products.
➢ The signal is amplified by electronic and displayed.
 CHROMATOGRAPH

Two types of detectors in Gas Chromatography (page 1311 Vol 1)

I. Thermal Conductivity Detector (TCS)

II. Flame Ionization Detector (FID)

Thermal Conductivity Detector (TCS) - Click Here

Rx R3

CO2

Working Principle of Thermal Conductivity Detector

▪ Tungsten elements act as a resistive element when electrical current is passed through it.
▪ There is a gas inside the chamber.
▪ Reference Gas ensures that there is a constant stable reference signal for constant calibration.
▪ The Reference Gas is a constant and is allowed to pass through the Tungsten even if temperature changes.
▪ The TCS has a Wheatstone Bridge arrangement.
▪ There is a DC supply.
▪ The R1 and R2 are constant and the same.
▪ R3 is Reference Gas and Rx is measuring resistance.
▪ CO2 will be vented out and there will be a new gas coming in.
▪ Because of the new gas RX will change, therefore generating different voltages in mV.
Flame Ionization Detector (FID) - Click Here

Advantage− Gives rapid results.

Disadvantage− This cannot be used in an explosive environment.

Working Principle of Flame Ionization Detector (FID) - Click Here

▪ The gas comes from the Column into the Tube
▪ At the end of the tube there is a Flame and a Metal Plate connected to an Electrode
▪ The Metal Tube around gas from the Column is connected to the negative Electrode.
▪ There is Carrier Gas(H2) which will move the gas from the Column into the Metal Plate for them to be Ionized by
the flame (Burning Process/Ionization)
▪ Different gases will be expelled/vented out at different points in time.
▪ The flame will be more brighter if a certain gas is present.
▪ Different signals will be generated by the ionization process.

ELECTROMAGNETIC ENERGY (Page 1191 Vol 1, Section 8.52, 8.61)

▪ Gamma-Rays – because gamma rays are small in wavelength they are used in nuclear applications because it can
penetrate through thick objects.
▪ X-Ray used in medical fields to check human skeleton bones. Can penetrate through human flesh and give read
out.
▪ As the wavelength gets larger it has its own specific uses
▪ Visible Light Spectrum – visible light for electromagnetic energy in terms of the visible light is only a small portion.
▪ It is between 400 mm and 700 mm which is the normal light spectrum than can be seen by humans.
How Visible Light/Spectrum is Used
▪ Energy is absorbed by gases or reflected by solids, in terms of light energy.
▪ If a light beam is passed through a gas, it will be absorbed, if it is passed through a solid it will be reflected.
▪ If a light beam directed towards a liquid, it will be reflected but the light beam will change angle.
▪ Example of infrared absorbed by Carbon Monoxide; IR has a wavelength of 25 µm – 2.5 µm
▪ IR light will be passed through cavity.
▪ The wavelength is absorbed by CO at 5 µm, the absorption increases, The absorption increases at 5 µm from more
less 0 to 0.5 and IR will be absorbed at 5 µm.
▪ The detector will pick up the amount of energy received.
▪ This is a Quantitative Measurement

Lambert-Beer Law
❖ The Beer-Lambert law states that there is a linear relationship between the concentration and the absorbance
of the solution, which enables the concentration of a solution to be calculated by measuring its absorbance.
IR SINGLE BEAM
➢ Sample of gas enter the Window Cell; sample is continuously passed through the Window Cell.
➢ Rotating Chopper Disc which is a Reference with Waveband Filter
➢ It gives a known reference to work from
➢ Measuring Waveband Filter - is the known wavelength for a specific type of gas.
➢ Rotating Chopper Disc will rotate, the detectors detect the Light Source.

Working principle of IR Single Beam

▪ As the Chopper spins from one filter to the other in an optical path, the difference in ratio in the energies received
at the detector will be a function of the concentration of the COI.
▪ Dirt on the window of the sample cell must not be allowed.

REFRACTOMETERS
➢ Use refraction principles to determine sample.
➢ Refraction Index (RI) and Refraction Angle (RA)

Example
o Three beaks filled with water and sugar,
o If we stick three sticks, they will appear more bent in the beaker with more sugar.

Velocity of light in vacuum

𝑅𝐼 = Velocity of light in sample

➢ Velocity of light in vacuum = 0.3 billion m/s RI = 1.0003 in air.

➢ RI = 2-3 in most liquids, solids, and gases.
SINGLE PASS DIFFERENTIAL REFRACTOMETER
➢ The reference cell is filled with a solution

Working principle Single Pass Differential Refractometer

▪ Sample goes in after conditioning and cleaning in the correct speed, phase and temperature.
▪ sample comes into the cavity.
▪ Since there is a gas on the cavity, the higher the concentration the more the angle will be Deflected and vice versa.
▪ Light is Reflected at the Differential Angle, then goes to the Beam Splitter.
▪ Photon Detector (which is a light sensitive electronic device) picks up the Angles of Refraction.
▪ Differential Amplifier gives an output by comparing Photon Detectors.

ELECTROCHEMICAL SENSORS
➢ Measures COI composition or concentration by detecting the changes in voltage or current that occur between
two electrodes in a solution over time.
➢ It is invasive measuring technique while light is non-invasive.

Selected Analysers
Oxygen (O2) measurement.
Conductivity.
pH
Moisture.
Oxygen Measurement (Section 8.42)
➢ Common in boiler systems where the combustion processes running require air in the boiling process.

Zirconium Oxide

Reference Gas

Working principle of Zirconium Oxide Layer

▪ Zirconium Layer is fused or welded on the pipe.
▪ When heated the oxygen ions will ionise then move through this Zirconium Oxide Layer
▪ Ions will move to a low concentration/Reference Gas, current flow with develop.
▪ Potential/emf will develop and measured by the Voltmeter.
▪ The emf corresponds to the amount of oxygen present and is used to determine the oxygen concentration.

Conductivity Measurement (Section 8.17)

➢ Used for water analysis.
➢ If we have equal jars of water, put one spoon of salt on the first jar, put two spoons of salt on the second jar, and
the three spoons of salt on the third jar.
➢ Each of the jar will have different concentration or conductivity levels
➢ If their resistance is measured in each jar, the resistance will decrease from 1 to 3 because of the amount of salt
increasing.
➢ Conductivity increases, Resistance decreases.
➢ Conductance is in Siemens
➢ Conductivity is needed because in an industrial environment the conductivity of water has to be known more
conductivity more salt.
 Electrodes

❖ The amount of ion energy that flow through is indirectly proportional to the conductance of the liquid.
▪ Voltage (E) is applied across the two electrodes from the power source. This creates an electric field within the
material between the electrodes.
▪ Due to the applied electric field, charge carriers (such as electrons or ions) within the material move, creating an
electric Current (I). This current is directly proportional to the conductivity of the material.
▪ The current flowing through the circuit is measured.
▪ The conductivity of the liquid is then calculated using the known values of applied Voltage (E), measured Current
(I), Distance Between the Electrodes (d), and the Area of The Electrodes (a).
𝑰⋅𝒅
𝝈=
𝑬⋅𝒂
Electrodeless Cell (page 1360 Vol 1, Section 8.17)

Working principle of an Electrodeless Cell

▪ As the liquid goes to The Cell Bore, (liquid is conductive)

▪ Primary Toroid generates a Magnetic Field because it is charged
▪ The Magnetic Field couple itself into the liquid passing through the Cell Bore
▪ Depending on how conductive the liquid is, it will induce emf around the
Secondary Toroid
▪ There are plates involved with the sample
pH Measurement (page 1607 Vol 1, Section 8.48)
➢ The Ph Measuring Transducer is a device used to measure the acidity or alkalinity of a solution based on its
hydrogen ion concentration.
➢ pH detectors belong to the ion-selective electrodes.
➢ Used in water treatment.
➢ pH devices work on electrochemical changes.

Working Principle of pH Measurement Transducer

▪ The transducer contains a glass pH Electrode that is sensitive to Hydrogen Ion concentration in the solution.
▪ The electrode typically consists of a Glass Membrane with a Reference Electrode inside, immersed in the solution
being measured.
▪ When the Glass Membrane comes into contact with the solution, Hydrogen Ions in the solution exchange with
sodium ions inside the Glass Membrane.
▪ This ion exchange process generates an electrical potential across the glass membrane, known as the
electromotive force (EMF)
Moisture In Air Measurement (Page 1472 8.32)
➢ Used for air tracking to determine the amount of moisture in air.
➢ Used to measure air flowing in a control valve for instrument device, we must know how much moisture is there.

Working Principle of Moisture in Air Measurement – Click Here (Dew Point Method)
▪ The gas comes in, there is a Mirror or chilled device which can reflect.
▪ Light Source shines on the mirror
▪ There is a cooling element and Peltier Heat Pump.
▪ Peltier Element has two metals welded together at common point which is a core junction.
▪ If heat is applied EMF will be generated.
▪ With Peltier the Element voltage is applied to it
▪ The cooling effect is done if there are multiple Peltier connected.
▪ The Mirror will cool down, if the gas has any moisture it will condense on the mirror
▪ The more moisture condensed on the mirror, the more the reflection of the light will be blocked out.
▪ The reflected light will be detected.

Mass Spectrometry (Section 8.29)

➢ Consists of an ion source, mass amplifier and detector.

➢ Used to identify the type and amount of chemical present in a sample by using mass to charge ratio.
➢ It is a Qualitative Measurement
➢ It is fast and can measure up to 12 Component Of Interest in five seconds
Working Principle of Mass Spectrometry
▪ Gas inflow - sample comes into the Ionizing Filament and Electron Trap
▪ Ionizing Filament gives off electrons.
▪ Electrons from the Filament pass through, to the Electron Trap knocking the electrons on off the Gas.
▪ Gas becomes positively charged.
▪ Beam Focus/Magnets allow the positively charged Gas molecules to be focused straight on the path.
▪ Ion Accelerator accelerates the positively charged gas molecules.
▪ Gases separate, particle with a heavier mass charge ratio will move to the top.
▪ The gases are collected, and a signal is amplified.
▪ Ratio output tell the gases present.

1.10 ANALYZER SELECTION PROCESS

➢ Problem Definition – benefit of measurement, is the cost justified? Use for closed loop control?
➢ Gathering Of Process Info – reasons (environment, safety, quality), gas or liquid, location of probes, sampling
methods.
Analyzer Selection Checks
Components Of Interest (COI)
Pressure And Temperature
Cross Sensitivity
Frequency Of Calibration
Drift
Noise.

➢ Sampling –Continuous or discrete? Probe cleaners, probe automation, filters?

➢ Analyzer location – Transportation lag, sample line diameter and length important factor. Analyzer housing cost.
Heating/cooling jackets. EX zone?
➢ Data handling – local or remote display? Special inputs to control system, alarms, etc.
➢ Maintenance – Spare parts, special test equipment, calibration standard cost and shelf life, training
requirements?