ro ep in ten 001 01 e_measuring parameters data collection and transmission

OMV Petrom S.A. Regulation

OMV Petrom S.A. Standard – RO-EP-IN-TEN-001-01-E Valid from: 07/02/2012

Concept study of 23 Edition: 01

TABLE OF CONTENTS

1.0 INTRODUCTION.......................................................................................................3 1.1 Context and Background ...........................................................................................3 1.2 Annex List ...............................................................................................................3 1.3 Abbreviations and Definitions ....................................................................................3 1.4 Scope .....................................................................................................................4

2.0 QUANTITIES AND UNITS ..........................................................................................4 2.1 General...................................................................................................................4 2.2 ISQ and SI...............................................................................................................5

2.2.1 SI Base Units ....................................................................................................5 2.2.2 SI Derived Units................................................................................................6 2.2.3 The unit one .....................................................................................................8 2.2.4 Other units .......................................................................................................8 2.2.5 SI prefixes........................................................................................................8

2.3 Quantities and units used in OMV PETROM .................................................................9 2.4 Conversions .......................................................................................................... 13

3.0 MEASUREMENT DEVICES AND DATA TRANSMISSION .............................................. 17 3.1 General................................................................................................................. 17 3.2 Measurement and data transmission in OMV PETROM................................................ 18

3.2.1 OMV PETROM’s and OMV’s Standards, Specifications and Philosophies ................ 18 3.2.2 Concept approach ........................................................................................... 19 3.2.3 Application areas ............................................................................................ 19 3.2.4 Fluid types ..................................................................................................... 20 3.2.5 Minimal measuring requirements. Data transmission........................................... 20 3.2.6 Specific measuring requirements for superior fields. Data transmission ................. 21

4.0 BIBLIOGRAPHY ...................................................................................................... 22 5.0 OBSOLETE REGULATIONS ...................................................................................... 23




1.0 INTRODUCTION

1.1 Context and Background

Petrom, a member of the OMV Group, is the largest oil and gas producer in South Eastern Europe. In Romania, Petrom is the sole crude oil producer and accounts for approximately half of the Romanian gas production. Petrom Exploration and Production business explores for and extracts oil and natural gas in Romania and other countries in the Caspian region.

The total domestic oil and gas production amounted in 2010 to around 173,900 boe/day (82,200 boe/day – oil and 91,700 boe/day – gas) while total proved oil and gas reserves were approximated to 832 mn boe (Romania: 805 mn boe) at the end of December 2010.

In Romania, Petrom holds exploration licenses for 15 onshore and 2 offshore blocks, with a total area of 59,100 km2 (of which 13,730 km2 is offshore) and operates 255 commercial oil and gas fields.

Continuous revisions of mature fields, achievement of the drilling program combined with diversification of the recovery mechanisms applied in 2010 led to an increase of the reserve replacement rate in Romania from 70% in 2009 to 72% in 2010. Petrom Group reserve replacement rate decreased to 67% due to reserves revisions in Kazakhstan.

Petrom intention is to develop an instrumented based measuring concept in order to minimize the errors caused by human interferences in the measuring processes and to monitor these processes locally and remotely.

1.2 Annex List

1. Annex A – Orientation table for flow meters 2. Annex B – Orientation table for level transmitters 3. Annex C – Orientation table for temperature sensors 4. Annex D – Orientation table for pressure detectors 5. Annex E – Orientation table for density sensors 6. Annex F - Orientation tables for safety and miscellaneous sensors 7. Annex G - Orientation tables for analytical instrumentation

1.3 Abbreviations and Definitions

BOE – Barrel of Oil Equivalent; BS&W – Basic Sediments and Water; CGPM – General Conference of Weights and Measures; CGS – Centimetre Gram Second System of Units (Metric System of Physical Units); CHP – Combined Heat and Power; CIPM – Comité International des Poids et Mesures; EN – European Norms; EUROSTAT – Statistical Office of the European Communities;




FGS – Fire and Gas System; G2P – Gas to Power; HART protocol – High Addressable Remote Transducer protocol; IEC – International Electrotechnical Commission; I/O – Input/Output; IRS – Internal Revenue Service; ISQ – International System of Quantities; ISO – International Organization for Standardization; IUPAC - International Union of Pure and Applied Chemistry; LCD - Liquid Cristal Display; OIML – Organisation Internationale de Métrologie Légale; PCS – Process Control System; PIMMS - Production Information Management and Monitoring System; PMAN – Production Manifold; SCADA – Supervisory Control And Data Acquisition; SI – The International System of Units; SIS – Safety Instrumented System; TOE – Tonne of Oil Equivalent VPN – Virtual Private Network; Shall – The word “shall” is used where a provision is mandatory; Should – The word “should” is used where a solution is preferred; May – The word “may” is used where alternatives are equally accepted;

1.4 Scope

The main goal of this concept is to serve as a guideline for selecting the suitable measurement devices for different process parameters in facilities belonging to different field ranks. The secondary goal is to link all OMV PETROM facilities to a future remote data acquisition and control system.

2.0 QUANTITIES AND UNITS

2.1 General

Quantities are related through equations that express laws of nature or define new quantities. Each equation between quantities is called a quantity equation.

It is convenient to consider some quantities of different kinds as mutually independent. Such quantities are called base quantities. Other quantities, called derived quantities, are defined or expressed in terms of base quantities by means of equations.

It is a matter of choice how many and which quantities are considered to be base quantities. It is also a matter of choice which equations are used to define the derived quantities. Each set of non-contradictory equations between quantities is called a system of quantities.




Units might be chosen arbitrarily, but making an independent choice of the unit for each quantity would lead to the appearance of additional numerical factors in the numerical value equations.

It is possible, however, and in practice more convenient, to choose a system of units in such a way that the numerical value equations have exactly the same form, including the numerical factors, as the corresponding equations in a chosen system of quantities. To establish such a system of units, first one and only one unit for each base quantity is defined. The units of the base quantities are called base units. Then, the units of all derived quantities are expressed in terms of the base units in accordance with the equations in the system of quantities. The units of the derived quantities are called derived units.

2.2 ISQ and SI

The special choice of base quantities and quantity equations, including multipliers, given in ISO 80000 and IEC 80000 defines the International System of Quantities, denoted “ISQ” in all languages. Derived quantities can be defined in terms of the base units by quantity equations. There are seven base quantities in the ISQ: length, mass, time, electric current, thermodynamic temperature, amount of substance, and luminous intensity.

The International System of Units, denoted SI in all languages, was adopted by the 11th International Conference on Weights and Measures, CGPM [1960] (Conférence générale des poids et mesures). The SI is a coherent system of units with respect to the ISQ. The SI comprises the base units and derived units that together form the coherent system of SI units.

In a coherent system of units, the expression of each unit corresponds to the dimension of the quantity in question, i.e. the expression of the unit is obtained by replacing the symbols for base dimensions in the quantity dimension by those for the base units, respectively. In particular, a quantity of dimension one acquires the unit one, symbol 1. In such a coherent system of units, no numerical factor other than 1 ever occurs in the expressions for the derived units in terms of the base units.

The units of measurement are categorized as follows:

2.2.1 SI Base Units

The seven SI base units are listed in Table 1.

Table 1 – SI base units for ISQ base quantities

ISQ Base quantity SI unit Symbol

Length Metre m Mass Kilogram kg Time Second s Electric current Ampere A Thermodynamic temperature Kelvin K Amount of substance Mole mol Luminous intensity Candela cd




2.2.2 SI Derived Units

The units derived coherently from SI base units are given as algebraic expressions in the form of products of powers of the SI base units with a numerical factor equal to 1.

SI derived quantities and units with special names and symbols are listed in Table 2. Table 3 contains SI derived units with special names and symbols admitted for reasons of safeguarding human health. Table 4 contains some common SI derived units without special names and symbols.

Table 2 — SI derived units with special names and symbols

ISQ derived quantity SI unit Symbol Formula expressed in SI base units

Formula expressed in SI base units and SI derived units

Plane angle Radian rad m·m-1= 1 m·m-1= 1

Solid angle Steradian sr m2·m-2= 1 m2·m-2= 1

Frequency Hertz Hz s-1 s-1 Force Newton N m·kg·s-2 m·kg·s-2 Pressure, stress Pascal Pa m-1·kg·s-2 N·m-2 Energy Joule J m2·kg·s-2 N·m Power(1) Watt W m2·kg·s-3 J·s-1 Electric charge Coulomb C A·s A·s Electric potential difference

Volt V m2·kg·s-3·A-1 W A-1

Capacitance Farad F m-2·kg-1·s4·A2 C V-1 Electric resistance Ohm Ω m2·kg·s-3·A-2 V A-1 Electric conductance Siemens S m-2·kg-1·s3·A2 Ω-1 Magnetic flux Weber Wb m2·kg·s-2·A-1 V s Magnetic flux density Tesla T kg·s-2·A-1 Wb m-2 Inductance Henry H m2·kg·s-2·A-2 Wb A-1 Celsius temperature Degree

Celsius ˚C K K

Luminous flux Lumen lm cd·sr cd·sr Illuminance Lux lx m-2·cd·sr lm·m-2 (1) Special names for the unit of power: the name volt−ampere (symbol ‘VA’) when it is used to express the apparent power of alternating electric current, and var (symbol ‘var’) when it is used to express reactive electric power. The ‘var’ is not included in CGPM resolutions.

Table 3 — SI derived units with special names and symbols admitted for reasons of safeguarding human health

ISQ derived quantity SI unit Symbol Formula expressed in SI base units


Activity (of a radionuclide)

Becquerel Bq s-1 s-1




Absorbed dose, specific energy imparted, kerma, absorbed dose index

Gray Gy m2·s-2 J·kg-1

Dose equivalent Sievert Sv m2·s-2 J·kg-1 Catalytic activity Katal kat mol/s mol/s

Table 4 - SI derived units without special names and symbols ISQ derived quantity

SI unit Symbol Formula expressed in SI base units


Area Square metre − m2 m2 Volume Cubic metre − m3 m3 Velocity Metre per

second − m·s-1 m·s-1

Acceleration Metre per second squared

− m·s-2 m·s-2

Flow rate Cubic metre per second

− m3·s-1 m3·s-1

Moment of mass

Kilogram metre − kg·m kg·m

Density Kilogram per cubic metre

− kg·m-3 kg·m-3

Concentration Gram per litre − 10-3·kg·l-1 10-3·kg·l-1 Momentum Kilogram metre

per second − kg·m·s-1 kg·m·s-1

Moment of inertia

Kilogram square metre

− kg·m2 kg·m2

Moment of force, torque

Newton metre − m2·kg·s-2 N·m

Viscosity (dynamic)

Milipascal second

− 10-3·m-1·kg·s-1 10-3·Pa·s

Viscosity (cinematic)

Square millimetre per second

− 10-6·m·s-1 10-6·m·s-1

Thermal conductivity

Watt per metre Kelvin

− m·kg·s-3·K W·m-1 K-1

Coefficient of heat transfer

Watt per square metre Kelvin

− kg·s-3·K W·m-2 K-1

Heat capacity Kilojoule per Kelvin

− 103·m2·kg·s-2·K-1 103·J·K-1

Specific heat capacity

Kilojoule per kilogram Kelvin

− 103·m2·s-2·K 103·J·kg-1·K-1

Entropy Kilojoule per Kelvin

− 103·m2·kg·s-2·K 103·J·K-1

Specific Kilojoule per − 103·m2·s-2·K 103·J·kg-1·K-1




entropy kilogram Kelvin Specific internal energy

Kilojoule per kilogram

− m2·s-2 103·J·kg-1

Magnetic field strength

Ampere per metre

− A·m-1 A·m-1

Electric resistivity

Ohm metre − m3·kg·s-3·A-2 Ω·m

Electric conductivity

Siemens per metre

− m-3·kg-1·s3·A2 S·m-1

Luminance Candela per square metre

− cd·m-2 cd·m-2

Wavelength Nanometre − 10-9·m 10-9·m

2.2.3 The unit one

The coherent SI unit for any quantity of dimension one is the unit one, symbol 1. It is generally not written out explicitly when such a quantity is expressed numerically.

Example 1 Number of turns in a winding N = 25 × 1 = 25

2.2.4 Other units

There are certain non-SI units that are recognized by the International Committee for Weights and Measures, CIPM (Comité International des Poids et Mesures), as having to be retained for use together with the SI (e.g. units of time (minute, hour and day), unit of volume (litre), unit for mass (tonne), unit for energy (electron volt)).

There are also certain non-SI units that are recognized by the CIPM to be used temporarily together with the SI (e.g. unit for pressure (bar)).

Some units for special purposes are adopted by ISO, IEC or OIML, such as the var, symbol var, (1 var: = 1 V · A) for reactive power. Other units and names of units are permitted in specialized field only (e.g. unit for vergency of optical systems (dioptre), unit for mass of precious stones (metric carat), unit for blood pressure and pressure of other body fluids (millimetre of mercury)). Many other units exist, e.g. atomic units, CGS units, Imperial units and US customary units. Except for the atomic units, the use of all such units is deprecated.

2.2.5 SI prefixes

In order to avoid large or small numerical values, decimal multiples and submultiples of the coherent SI units are formed with the SI prefixes listed in Table 5. These SI multiple units and SI sub-multiple units are not coherent with respect to the ISQ.

Table 5 - SI prefixes

Prefix Factor

Name Symbol




1024 yotta Y 1021 zetta Z 1018 exa E 1015 peta P 1012 tera T 109 giga G 106 mega M 103 kilo k 102 hecto h 101 deca da 10-1 deci d 10-2 centi c 10-3 milli m 10-6 micro μ 10-9 nano n 10-12 pico p 10-15 femto f 10-18 atto a 10-21 zepto z 10-24 yocto y The symbol of a prefix is considered to be combined with the single unit symbol to which it is directly attached, forming with it a new symbol for a decimal multiple or sub-multiple that can be raised to a positive or negative power and that can be combined with other unit symbols to form symbols for compound units.

2.3 Quantities and units used in OMV PETROM

The most common quantities and units met in OMV PETROM are listed in Table 6. The preferred units belong to SI and the tolerated units are linked to other measurement systems.

Table 6 – Preferred and tolerated units Quantity Preferred unit Tolerated unit

Quantities of Space and Time Length Length metre (m)

millimetre (mm) inch (in) mil (mil)

Area Area square metre (m2)

acre hectare (ha)

−

Volume Volume (actual) cubic metre (m3)

cubic centimetre (cm3) litre (l)

barrel (bbl) (API)

Volume (normal)1) normal cubic metre (Nm3) −




Volume (standard)2) standard cubic metre (Sm3) −

Time Time second (s)

minute (min) hour (h) day (d)

−

Frequency Frequency hertz (Hz) revolutions per minute (rpm) Velocity Velocity metre per second (m/s)

kilometre per hour (km/h) −

Acceleration Acceleration Metre per second squared −

Flow rate Gas mass flow rate kilogram per day (kg/d)

kilogram per hour (kg/h) −

Gas volumetric flow rate (actual)

cubic metre per day (m3/d) −

Gas volumetric flow rate (normal)1)

normal cubic metre per day (Nm3/d)

−

Gas volumetric flow rate (standard)2)

standard cubic metre per day (Sm3/d)

−

Liquid mass flow rate kilogram per day (kg/d) kilogram per hour (kg/h)

−

Liquid volume flow rate cubic metre per hour (m3/h) litre per hour (l/h)

−

Fuel efficiency Fuel efficiency Kilometre per litre (km/l)

Quantities of Mechanics Acidity/basicity Acidity/basicity pH − Amount of substance Amount of substance mole (mole) − Mass Mass kilogram (kg)

tonne (to) −

Moment of mass Moment of mass kilogram metre (kg·m)

Density Density kilogram per cubic metre

(kg/m3) −

Specific gravity Specific gravity SG (1) API gravity (°API) Concentration (mass) Concentration gram per litre (g/l) −




Force Force newton (N) −



newton metre (N·m)

Pressure, stress

Pressure (differential) kilopascal (kPa) bar (bar) millibar (mbar) millimetre of water column (mmH2O)

−

Pressure (gauge) bar gauge (barg) − Pressure (absolute) bar absolute (bara) − Viscosity (dynamic) Viscosity (dynamic) pascal second (Pa·s)

milipascal second (mPa·s) poise (P) centipoise (cP)

Viscosity (cinematic) Viscosity (cinematic) square metre per second (m2/s)

square millimetre per second (mm2/s)

stokes (St) centistokes (cSt)

Energy, work, heat

Energy Megawatt hour (MWh) Gigajoule (GJ) Gigacalorie (Gcal)

tonne of oil equivalent (toe) barrel of oil equivalent (boe) British thermal unit (Btu)

Power Power Megawatt (MW)

Gigajoule per hour (GJ/h) Gigacalorie per hour (Gcal/h)

horsepower (HP) Btu per hour

Quantities of heat Temperature Temperature Celsius degree (°C) − Thermodynamic temperature

Kelvin (K) −

Thermal conductivity Thermal conductivity Watt per metre Kelvin (W/m·K) − Coefficient of heat transfer

Coefficient of heat transfer

Watt per square metre Kelvin (W/m2·K)

−

Heat capacity

Heat capacity kilojoule per Kelvin ((kJ/K)) − Specific heat capacity

Specific heat capacity kilojoule per kilogram kelvin




(kJ/kg·K)

Entropy Entropy kilojoule per Kelvin (kJ/K)

Specific entropy Specific entropy kilojoule per kilogram kelvin

(kJ/kg·K)

Specific internal energy Specific internal energy kilojoule per kilogram (kJ/kg)

Quantities of Electricity and Magnetism Electric current Electric current ampere (A) − Electric resistance Electric resistance ohm (Ω) − Electric potential difference

Electric potential difference

volt (V) −

Electric resistivity Electric resistivity Ohm metre (Ω·m) − Electric conductivity Electric conductivity microsiemens per centimetre

(μS/cm ) millisiemens per centimetre (mS/cm)

−

Magnetic field strength Magnetic field strength ampere per metre (A/m)

Magnetic flux Magnetic flux nanoweber (nWb)

Magnetic flux density Magnetic flux density millitesla (mT)

Quantity of Light and Related Electromagnetic Radiation Wavelength Wavelength nanometre (nm) − Luminance Luminance candela per square metre

(cd/m2)

Luminance exitance Luminance exitance lux (lx) Illuminance Illuminance lux (lx) Notes: 1) Normal conditions are: temperature = 0˚C, pressure = 1.01325 bara 2) Standard conditions are: temperature = 15˚C, pressure = 1.01325 bara




The company production profiles are provided in SI units, as follows: gross oil production in m3/d, net oil production in to/d, gas flow in Nm3/d or Sm3/d and water injection rate in m3/d. The multiple of units used for company production are: x1,000 (k (kilo) or M (thousand)) and x1,000,000 (MM (million)).

2.4 Conversions

Conversion between SI units and other measurement systems units are given below:

Length kilometre (km)

metre (m) millimetre (mm)

micrometre (μm)

inch (in) mil (mil)

metre (m) 0.001 1 1,000 1,000,000 39.36996 39370.1 millimetre (mm)

0.000001 0.001 1 1,000 0.03936996 39.3701

micrometre (μm)

0.000000001 0.000001 0.001 1 0.000039367 0.0393701

inch (in) 0.0000254 0.0254 25.4 25,400 1 1,000 mil (mil) 0.0000000254 0.0000254 0.0254 25.4 0.001 1 Note: “Kilometre” is used for long distances (flow line and pipeline lengths); “Metre” is generally used for measuring the vessel sizes (diameter, length and height); “Millimetre” and “inch” are used for the corrosion allowance of the vessel and piping walls, for the piping, valve, flange sizes; “Millimetre”, “micrometre” and “mil” are used in the condition monitoring of the rotary machines (axial and radial vibration); Volume cubic metre

(m3) cubic

centimetre (cm3)

litre (l) barrel (bbl) (API)

cubic metre (m3)

1 1,000,000 1,000 6.29

cubic centimetre (cm3)

0.000001 1 0.001 0.00000629

litre (l) 0.001 1,000 1 0.00629 barrel (bbl API) 0.158987 158,987 158.987 1 Note: “Cubic metre” is specially used for the definition of the big spaces, like the vessel volume; “Cubic centimetre” is used for the laboratory issues, the metering pump matters; “Litre” is used in the metering pump applications; “Barrel” is specially used for the oil production report; Time second (s) minute (m) hour (h) day (d) second (s) 1 0.166 0.000277 0.0000115 minute (m) 60 1 0.0166 0.000694 hour (h) 3,600 60 1 0.0416 day (d) 86,400 1,440 24 1




Note: “Second” is generally used for the velocity calculation in the flow lines, pipelines and piping; “Minute” is used for the metering pump applications, the laboratory issues; “Hour” and “day” are generally used in the calculation of the big flow rates; Frequency hertz (Hz) revolutions per minute (rpm) hertz (Hz) 1 0.0166667 revolutions per minute (rpm)

60 1

Note: “Hertz” is generally used in the electrical field (alternative current); “Rpm” is used for the rotary machines; Specific gravity SG (1) API gravity (°API) SG (1) 1 141.5/(131.5+°API) API gravity (°API)

141.5/SG-131.5 1

Note: “SG” is the ratio of the density (mass of a unit volume) of a substance to the density (mass of the same unit volume) of a reference substance. The reference substance is nearly always water for liquids or air for gases. The American Petroleum Institute gravity, or “API gravity”, is a measure of how heavy or light a petroleum liquid is compared to water; If its API gravity is greater than 10, it is lighter and floats on water; if less than 10, it is heavier and sinks. The formula is: API gravity = (141.5/SG)-131.5 The most used is “SG”. Pressure Pascal

(Pa) kilopascal

(kPa) bar millibar

(mbar) mmH2O

pascal (Pa) 1 0.001 0.00001 0.01 0.1019716213 kilopascal (kPa)

1,000 1 0.01 10 101.9716213

bar 100,000 100 1 1,000 10,197.16213 millibar (mbar)

100 0.1 0.001 1 10.19716213

mmH2O 9.80665 0.00980665 0.0000980665 0.0980665 1 Note: “Pascal” and “kilopascal” are mostly used in the calculations; “Bar” is a practical unit, even though it is not a SI unit; “Millibar” and “mmH2O” are used for the small pressure measurement (e.g. combustion chamber into the heater) or level measurement by means of the differential pressure; Flow rate Normal cubic metre per day

(Nm3/d) Standard cubic metre per day

(Sm3/d) Normal cubic metre per day

1 0.948




(Nm3/d) Standard cubic metre per day (Sm3/d)

1.055 1

Note: These two units are used for the gas flow rates and refer to the normal and standard conditions (see previous chapter). Viscosity (dynamic)

pascal second (Pa·s)

millipascal second (mPa·s)

poise (P) centipoise (cP)

pascal second (Pa·s)

1 1,000 10 1,000

millipascal second (mPa·s)

0,001 1 0.01 1

poise (P) 0.1 100 1 100 centipoise (cP) 0.001 1 0.01 1 Note: “Pascal second” and “millipascal second” are SI units and mostly used in the calculations; “Poise” (rarely) and “centipoise” (often) are practical units, even though they are not SI units;

Viscosity (cinematic)

square metre per second

(m2/s)

square millimetre per

second (mm2/s)

stokes (St) centistokes (cSt)

square metre per second (m2/s)

1 1,000,000 10,000 1,000,000

square millimetre per second (mm2/s)

0.000001 1 0.01 1

stokes (St) 0.0001 100 1 100 centistokes (cSt)

0.000001 1 0.01 1

Note: “Square metre per second” and “square millimetre per second” are SI units and mostly used in the calculations; “Stokes” (rarely) and “centistokes” (often) are practical units, even though they are not SI units;

Energy Megawatt hour (MWh)

Giga calorie (Gcal)

Giga joule (GJ)

Tonne of oil equivalent (toe)

Barrel of oil equivalent (boe)

British thermal unit (Btu)

Tonne of steam

Megawatt hour

1 0.86 3.6 0.086 0.5883 3,412,141.48 ~1.25




(MWh) Gigacalorie (Gcal)

1.16 1 4.184 0.1 0.6624 3,965,667 −

Gigajoule (GJ)

0.278 0.239 1 0.0239 0.1634 947,817.078 −

Tonne of oil equivalent (toe)

11.63 10 41.868 1 6.841 39,683,205.4 −

Barrel of oil equivalent (boe)

1.7 1.462 6.1178 0.146 1 5.8×106 −

British thermal unit (Btu)

2.9307 x10-7

25x10-8 1,055x10-9

2.52x10-8 0.17x10-6 1 −

Tonne of steam

~0.8 − − − − − 1

Note 1: “Megawatt hour” and “gigajoule” are the most used units for the energy; “Gigacalorie” is specially used by the thermal energy suppliers (e.g.; hot water supplied for the apartment heating); “Tonne of oil equivalent” (defined by EUROSTAT) is the amount of energy released by burning one tonne of crude oil, approximately 42 GJ (as different crude oils have different calorific values), the exact value of the toe is defined by convention. It is used for large amounts of energy, as it can be more intuitive to visualise. “Tonne of oil equivalent” is used to determine the energy of oil and gas production. “Barrel of oil equivalent” (defined by IRS) is the amount of energy released by burning one barrel of crude oil. Conversion between toe and boe are shown above. “Barrel of oil equivalent” is used to determine the energy of oil and gas production. “British thermal unit” is a traditional unit of energy equal to about 1055 joules. It is approximately the amount of heat required to raise the temperature of one 1 pound (0.454 kg) of liquid water by 1 °F (0.556°C) at a constant pressure of one atmosphere. The unit is most often used in the power, steam generation, heating and air conditioning industries. “Tonne of steam” is the amount of energy given by the total enthalpy of the steam as delivered, and subtract the enthalpy of the returned condensate (if returned) or of the water as it enters the boiler multiplied by mass (a tonne of water). The enthalpy depends by pressure and temperature that is why the “tonne of steam” does not have a unique determined value. As it is mentioned above this unit is used for the boiler applications. Note 2: The mass of a fuel gas volume (in normal or standard conditions) multiplied by calorific value is the gas energy.

Power Megawatt (MW)

Gicacalorie per hour (Gcal/h)

Gigajoule per hour (GJ/h)

BTU per hour (BTU/h)

Horsepower (HP)

Megawatt (MW)

1 0.8604 3.6 3412141.63 1,341.022




Gicacalorie per hour (Gcal/h)

1.162 1 4.184 3.965x106 1,550

Gigajoule per hour (GJ/h)

0.27 0.239 1 947,820 372.5

BTU per hour (BTU/h)

2.9307x10-7 252x10-9 105x10-8 1 39x10-5

Horsepower (HP)

74x10-5 641x10-6 2.684x10-3 2544.4335 1

Note: The power is the rate at which energy is transferred, used or transformed. The power units are the ratio between energy units (see table above) and time. A special power unit is “horsepower” which is equal with 740 Watt and it is specially used for the engine power.

Temperature Celsius (°C) Kelvin (K) Fahrenheit (°F) Celsius (°C) 1 [K]-273.15 ([°F]−32)×5⁄9 Kelvin (K) [°C]+273.15 1 ([°F]+459.67)×5⁄9 Fahrenheit (°F) [°C]×9⁄5+32 [K]×9⁄5−459.67 1 Note: “Celsius” unit is a practical unit, used mostly in Europe. “Kelvin” unit is a SI unit, but it is generally used in the calculations. “Fahrenheit” unit is a practical unit on American continent.

3.0 MEASUREMENT DEVICES AND DATA TRANSMISSION

3.1 General

In the physical sciences, quality assurance, and engineering, measurement is the activity of obtaining and comparing physical quantities of real-world objects and events. Established standard objects and events are used as units, and the process of measurement gives a number relating the item under study and the referenced unit of measurement. Measuring instruments, and formal test methods which define the instrument's use, are the means by which these relations of numbers are obtained. All measuring instruments are subject to varying degrees of instrument error and measurement uncertainty.

The measurement devices used in oil and gas industry can be found in Annexes A thru G and they are used for different applications: liquid, gas, steam, smoke, fire (see annexes). They are dedicated for measuring different parameters, like: flow, level, temperature, pressure, density, energy, safety parameters (gas, smoke and fire events), vibration, dimension, weight, analytical and many other parameters.

Three functions are characteristic for devices mentioned above: monitor & control, safety and fire & gas. Each function is carried out by an instrumented system, as follows: Process Control System (PCS), Safety Instrumented System (SIS) and Fire and Gas System (FGS). The logic solvers of these three systems are commonly independent and separated, but information interchangers. This system architecture is usually typical for each facility.




A higher management level is mandatory for data gathering from more unmanned facilities. Each unmanned facility is connected via a communication network to manned centres which can monitor and even control the processes in facilities allocated.

3.2 Measurement and data transmission in OMV PETROM

3.2.1 OMV PETROM’s and OMV’s Standards, Specifications and Philosophies

The concept is performed in accordance with OMV PETROM’s and OMV’s Standards, Specifications and Philosophies, as well as the provisions, norms and regulations referenced in following list.

INSTRUMENTATION EP FA IN 01 PH Philosophy for Instrumentation and Instrument Air EP FA IN 03 PH Philosophy for Flow Measuring Systems EP FA IN 04 PH Philosophy for Process Control Systems EP FA IN 05 PH Philosophy for Automation, Telecommunication and Security

Systems EP FA IN 06 PH Philosophy for Tank Instrumentation EP FA IN 07 PH Philosophy for Facilities Emergency Shut Down - Wellhead

Protection Systems EP FA IN 08 PH Philosophy for Artificial Lift Well's Protection Systems RO-EP-FE-IN-PHL-001-01 Philosophy for Control and Instrumentation in Packaged Units TO-HQ-02-021 Philosophy for Process Control Systems - Onshore TO-HQ-02-022 Philosophy for Wellhead Hydraulic Systems - Onshore TO-HQ-02-023 Philosophy for Safety Integrity Levels - Onshore TO-HQ-02-024 Philosophy for Emergency and Process Shutdown Systems -

Onshore TO-HQ-02-026 Philosophy for Communications and Security Systems -

Onshore TO-HQ-02-027 Philosophy for Flow Measuring Systems - Onshore ATEX EP FA FF 01 PH Philosophy for Fire and Gas Detection Systems EP FA HA 01 ST Company Standard for Areas Classification RO-EP-SR-STD-001-01 Company Standard for Selection of Ex Equipment TO-HQ-02-019 Philosophy for Hazardous Area Classification and HVAC -

Onshore TO-HQ-02-025 Philosophy for Fire and Gas Systems – Onshore PROCESS EP FA PS 01 ST Technical Requirements for Gas Metering Stations OPERATION-PRODUCTION PEP-PSR-POL-001-01.00 Physical Inventory taking of crude oil stocks PEP-PSR-PRO-002-01.00 Oil and gas wells production measurement




The most recent edition of the applicable standards will be used, which may be found on OMV PETROM intranet (REAL and/or EP Connect).

3.2.2 Concept approach

The concept is defined using oil or gas reservoir ranking which seems to be an acceptable instrument for concept development. Being a very large subject, the concept is split into two parts: the first one is dedicated to the stone & bronze reservoirs, while the second is dedicated to the silver, gold & platinum reservoirs.

The first part is dedicated to the least valuable reservoirs (in terms of production, production costs, expected life time and efficiency), that is why the concept requirements are “milder” and they will be classified as minimum requirements.

The second part is dedicated for the most valuable reservoirs (considering the same ranking criteria as above) and they will increase the class of requirements definitively. It is obviously that the concept requirements can not be the same for both of the reservoir ranks due to the cost differences in their implementation.

3.2.3 Application areas

The applicability range is referring to: the reservoir nature (oil or gas) and the production stream components (i.e. measuring approach for wells is different than measuring approach for tank farms).

The specific processes for oil stream are: production, transport, gathering, separation, heat & chemical treatment, storage and boost injection. Each process of oil stream is specific to one location or more (e.g. production is related to wells, gathering is linked to parks and tank farms, etc).

The components of oil stream can be simple, like wells, flow lines & pipelines or complex, like parks, PMAN, PMAN + test separators, tank farms, water injection stations, steam injection stations, gas & CO2 injection stations and air injection stations.

The specific processes for gas stream are: production, transport, gathering, separation, conditioning & compression. For remote gas wells where running flow lines is not a feasible solution, other process is fit for purpose: gas to power (G2P). Each process of the gas stream is specific to one location or more (e.g. production is related to wells, gathering is linked to parks and gas treatment & compression stations, etc).

The components of gas stream can be simple, like wells1), flow lines & pipelines or complex, like parks and conditioning & compression stations. Notes: 1) Three different well configurations may be found in OMV PETROM fields: - Standard wells – gas parameters (composition, pressure, flow, temperature, etc) do permit the gas transportation directly to parks; - Key wells – gas parameters (see above) do not permit the gas transportation directly to parks and a local facility is developed around the well; - G2P wells – the gas is transformed by a micro-turbine in the electric power;




3.2.4 Fluid types

Two fluid types are considered and defined below: - The process fluids - The utility fluids The process fluids are considered to be: - The fluids extracted from underground, processed and delivered to the third party; - The fluids already processed and injected into the reservoir for reservoir pressure maintenance; - The fluids transformed in energy (G2P, CHP); The utility fluids are considered to be: - The chemicals added to the process fluids for processing scope (O2 scavengers, corrosion inhibitors, anti-scalants, demulsifiers, antifoams, glycols, amines, etc); - The thermal agents (steam, hot water, etc); - The fuel gas, diesel fuel; - The blanketing gas; - The compressed air; - The inert gas; - The lube oil; - The electricity1); - Etc; Notes: 1) The electric energy can be a process fluid and/or a utility fluid. The energy production & consumption data base is managed by EDEN software application for each asset.

The fluid phase is other important factor that is taken into account. For instance, not all liquid flow measuring techniques are applicable for gas flow measuring and vice-versa.

3.2.5 Minimal measuring requirements. Data transmission

Minimal measurement device criteria are applied for the facilities allocated to the stone and bronze fields. These criteria are considered from both economical point of view and technical performances point of view as well.

From economical point of view, the most feasible devices shall be selected in projects (but in accordance to OMV PETROM philosophies and standards). For selection, see Annexes A thru G.

From technical performances point of view, the following criteria shall be applied for devices: 1. Remote/ local device use ratio: less than 1, i.e. more local indication than transmitters (remote devices to be installed in the vital points only) 2. On/off or continuous measurement: on/off is preferred (switches to be used as initiators devices) 3. Analytical device used: laboratory 4. Accuracy: technically justified 5. LCD local indicator (for transmitters): no 6. Transmitter output signal: 4-20 mA + HART hardwired 7. Electronics housing: metallic (polyurethane covered aluminium)




8. Cable glands: metallic (brass) 9. Special configuration (software and hardware): Standard 10. Special tests: Standard For selection, see Annexes A thru G.

The facility design shall be for unmanned activity. The simple facilities, like wells, flow lines and pipelines need, minimal instrumented systems, which can be connected to bigger neighbouring facilities (like parks, tank farms) via VPN.

The complex facilities, like parks, tank farms, water injection stations, etc, will have more sophisticate instrumented systems connected via VPN to a superior monitor and control level. Generally, complex facility logic solvers of PCS and SIS should be independent one each other, but can be combined (in special cases only and agreed by OMV PETROM) taken into account the most restrictive function (safety function). F&G logic solver is independent and separated by logic solvers of PCS and SIS. The logic solvers are able to use VPN network for data transmission scope. The data transmission will be defined by Global Solutions according to their standards.

The data management is done at asset and head quarter levels by a manned SCADA system. The other data management systems (PIMMS, EDEN, etc) shall be interfaced to SCADA system.

3.2.6 Specific measuring requirements for superior fields. Data transmission

Specific measurement device requirement criteria are applied for the facilities allocated to silver, gold and platinum fields.

From economical point of view, the entire price ranges are permitted. For selection, see Annexes A thru G.

From technical performances point of view, the following criteria are applied for devices: 1. Remote/ local device use ratio: at least 1 (remote devices are preferred to local devices) 2. On/off or continuous measurement: continuous is preferred (transmitters rather than switches) 3. Analytical device used: laboratory and on line 4. Accuracy: no restrictions 5. LCD local indicator (for transmitters): yes 6. Transmitter output signal: 4-20 mA + HART hardwired/wireless 7. Electronics housing: metallic (at least polyurethane covered aluminium) 8. Cable glands: metallic (at least brass) 9. Special configuration (software and hardware): no restrictions 10. Special tests: no restrictions For selection, see Annexes A thru G.

The facility design shall be for unmanned activity. The simple facilities, like wells, flow lines and pipelines need, minimal instrumented systems, which can be connected to bigger neighbouring facilities (like parks, tank farms) via VPN.




The complex facilities, like parks, tank farms, water injection stations, etc, will have more sophisticate instrumented systems connected via VPN to a superior monitor and control level. Generally, the complex facility logic solvers of PCS and SIS should be independent one each other, but can be combined (in special cases only and agreed by OMV PETROM) taken into account the most restrictive function (safety function). F&G logic solver is independent and separated by logic solvers of PCS and SIS. The logic solvers are able to use VPN network for data communication scope. The data transmission will be defined by Global Solutions according to their standards.

The data management is done at asset and head quarter levels by a manned SCADA system. The other data management systems (PIMMS, EDEN, etc) shall be interfaced to SCADA system.

4.0 BIBLIOGRAPHY

[1] EN/ISO 80000 – Quantities and Units

[2] SR ISO 31-0 – Marimi si Unitati – Institutul Roman de Standardizare

[3] NIST Special Publication 1038 - The International System of Units (SI) – Conversion Factors for General Use – Authors: Kenneth Butcher, Linda Crown, Elizabeth J. Gentry

[4] COUNCIL DIRECTIVE of 20 December 1979 on the approximation of the laws of the Member States relating to units of measurement and on the repeal of Directive 71/354/EEC

[5] DIRECTIVE 2009/3/EC OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL of 11 March 2009 amending Council Directive 80/181/EEC on the approximation of the laws of the Member States relating to units of measurement

[6] HG 755/2004 Approval of legal units of measurement

[7] The SI Metric System of Units and SPE Metric Standard – Society of Petroleum Engineers

[8] Instrument Engineers' Handbook Volume 1 4th Ed - Process Control and Optimization – Author: B. G. LIPTÁK

[9] Internet sites: www.wikipedia.com, www.thermexcel.com, www.spe.org, www.rapidlibrary.com, www.freeengineeringbooks.com, www.engineeringtoolbox.com, etc.

[10] ANRM Order 41/1998 Technical instructions for the activity of owner of oil & gas licenses

[11] ANRM Order 163/2010 Frame contract for the transportation of oil, gasoline, condensate and liquid ethane




[12] ANRE Order 62/2008 Regulation for the measurement of natural gas quantities

[13] ANRE Order 17/2002 Technical Code for the measurement of electrical energy

5.0 OBSOLETE REGULATIONS

None.

Orientation table for flow meters

Annex A of OMV Petrom S.A. Concept study – RO-EP-IN-TEN-001-01-E Edition 01 Valid from: 07/02/2012 Page 1 of 1

Elb

ow

Tap

s

Jet

Defl

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on

Lam

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Flo

wm

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rs

Mag

neti

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Mass

Flo

wm

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c.

Co

rio

lis

Mete

rin

g

Pu

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fice (

Pla

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ral C

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Po

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Dis

pla

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t G

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ve

Dis

pla

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uid

Mete

rs

Seg

men

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lid

s Flo

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ete

rs

Targ

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Mete

rs

Th

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al M

ete

rs

(Mass

Flo

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Flo

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Flo

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r

Ult

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nic

Flo

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t D

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Flo

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(Du

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Tu

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Flo

w N

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Vo

rtex

Sh

ed

din

g

Flu

idic

O

scilla

tin

g

Weir

s, F

lum

es

Clean liquids

√ √ √[5] √ √

√ √ √ √ √ √ √ √ √ √

√ √

√ √ √

√

Viscous liquids

L √ √[5] √ √

√ L √ √ Sd √ L L L L L

L L

L

Slurry L √[5] √ L

√ L L √ SD L L L √

L L L

L

Gas √ √ √ √ √

√ √ √ √ √ SD √ L

√ √ √

√

Field of applications

Solids SD √ L

Rangeability 3:1[9]

25:1 10:1 10:1[9] 100:1 20:1

20:1 3:1[9] 3:1[9] 10:1 to 200:1

10:1[9] 3:1 20:1 4:1 20:1[9] 10:1 (>100:1)

3:1[2] 20:1 10:1

5:1 (to 20:1)

3:1[2]

3:1[2 10:1[8]

20:1[8]

10:1[8]

100:1

Pressure loss thru sensor N N H H A H

— H M M H M — H A H M N N

A M H

H H H

M

Approx straight pipe-run requirement (upstream/ downstream diameters)

25/10[7] 20/5[7] 15/5 5/3 N N

N 20/5[7] 30/5[7] N N 15/5 5/3 20/5 5/3 15/5[7] 2/5 15/5[7]

15/5[7] N 15/5[7]

20/5[7 20/5 20/5 20/5

See text

Accuracy *±% Full range **±% Rate ***±% Registration

5÷10* 2* 0.5÷5*[10] 0.5**÷2* 0.5** 0.15÷0.5**

0.1÷1* 0.5**÷2* 0.5÷5* 0.5÷1*** 0.1÷2** 3** 0.5**÷4* 0.5*÷5* 1÷2* 0.25** 0.5÷2** 1**÷2* 2÷3*

0.5*÷10** 0.5**÷1* 1**÷2*

0.5÷1.5** 1÷2** 0÷5*

2÷5*

L = Limited SD = Some Designs H = High A = Average M = Minimal N = None SR = Square Root [1] = The data in this column is for general guidance only. [2] = Inherent rangeability of primary device is substantially greater than shown. Value used reflects limitation of differential pressure sensing device, when 1% of actual flow of accuracy is desired. With multiple-range intelligent transmitters the rangeability can reach 10:1. [3] = Pipe size establishes the upper limit. [4] = Practically unlimited with the probe type design. [5] = Must be conductive. [6] = Can be re-ranged over 100:1. [7] = Varies with upstream disturbance. [8] = Can be more at high Re. No. services. [9] = Up to 100:1 with high-precision design. [10] = Commercially available gas flow elements can be 1% of rate. [11] = More for gas turbine meters. Note: OMV PETROM uses three methods for the production calculation (in tonnes): - Laboratory analysis for water-cut determination (“hotoaica” or sampling system of the flowmeter) - Water-cut measurement (online water-cut meter) - Water-cut calculation (density method)

Orientation table for level transmitters

Annex B of OMV Petrom S.A. Concept study – RO-EP-IN-TEN-001-01-E Edition 01 Valid from: 07/02/2012 Page 1 of 1

Air

b

ub

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rs

Cap

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Pre

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Level

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Rad

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Rad

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(Ult

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TD

R

Th

erm

al

Dis

pers

ion

Max. temperature (°C) UL 1,100 175 650 450 260 150 370 260 UL 110 150 150 200 450

Non-contacting possible √ √ √ √ √

Accuracy-%Span 0.5÷1# 0.5÷3 1÷3# 0.25÷1# 0.25÷1# 0.1÷3 0.25 in.

[6 mm] 0.25 in.

[6 mm] 0.1÷1 1÷2 0.1÷1 0.25÷3 0.1 in.

[3 mm] 0.1÷2 1÷3#

Conducting E E L E E E L E E E E E E E E

Insulating E E/F L E E E L E L E E E E E E

Waterlike liquids

Interface NA E NA NA F L L L NA E/NA NA NA NA/F L NA

Conducting F NA/E F E L L E L E E L F F E F

Insulating F F/E F E L L E L L E L F F F F

Coating liquids

Aqueous slurries

NA NA/E NA NA NA NA E NA E L F NA NA E NA

Aqueous foams

IG ME IG IG IG IG/ME L L L L IG IG IG/ME ME IG/ME Foams

Organic foams

IG IG/ME IG IG IG IG/ME L L NA E IG IG IG/ME IG IG/ME

Powder NA L NA NA NA NA L NA E E NA NA NA/F E NA

Shunks NA L NA NA NA NA E NA L E NA NA NA/F E NA

Process materials

Solids

Sticky NA L NA NA NA NA E NA L E NA NA NA L NA

Comments/ Precautions

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it m

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big

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pro

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m.

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$300÷1,000 √ √ √ √ √ √ √

$1,000÷2,500 √ √ √ √ √ √ √ √ √ √ √ √ √ Cost

Over $2,500 √ √ √ √ √ √ √ √ √

E = excellent ME = measures foam L = limited models, geometry, or process media IG = ignores foam F = fair NA = not applicable UL = unlimited # = assuming constant density

Orientation table for temperature sensors

Annex C of OMV Petrom S.A. Concept study – RO-EP-IN-TEN-001-01-E Edition 01 Valid from: 07/02/2012 Page 1 of 2

Bim

etal

lic

Ele

men

ts

Colo

r In

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ents

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Vap

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Sp

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Py

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s

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neu

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Py

rom

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Rad

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Py

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s

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-

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Cry

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Bulb

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m

Th

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isto

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Th

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s

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yp

e T

- T

yp

e J

- T

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-

Typ

es R

& S

Ult

raso

nic

Under 38°C

√ √ —

√ √ — √

√ √ √

√ — √ √ — —

— √ — √ √ √

√

√ √ √ —

√

38°C to 538°C √ √ √ √ √ √

√ √ √

— √ — — — √

√ √

√ — √

√ √ √

√ √ √ √ √

√

Available span

Above 538°C — — √ — — √ √

— — —

— — — — √ —

√ √

— √ √

— — √

— — √ √ √

√

Accuracy (% full scale or % of span)

1÷2 — 1 0.5÷2 0.5÷2 0.5÷2 0.5÷2

0.1÷2 0.2÷2 2

— 2 — 1 1 —

2 2

— 1÷2 0.5÷2

0.1 0.25 0.15

0.2 0.1 0.1 0.1 0.1

5

Under $200 √ √ — √ √ √ √

√ — —

— — √ — — √

— —

√ — —

— √ —

√

√ √ — —

—

$200 to $1,000 — — — √ √ √ √

— √ √

√ √ — — — √

— —

— — —

— √ √

√

√ √ √ √

—

Cost

Above 1,000 — — √ — — — —

— — —

— — — √ √ —

√ √

— √ √

√ √ √

— — — — —

√

Stability

E — F E E E E

E G F

F,G F E G G —

F F

E F F

E G,E E

F G G G G

G

Repeatability

F — F F F F F

E G G

G F

G,E G,E G,E —

G G

F F F

G E E

G G G G G

F,G

Orientation table for temperature sensors

Annex C of OMV Petrom S.A. Concept study – RO-EP-IN-TEN-001-01-E Edition 01 Valid from: 07/02/2012 Page 2 of 2

Response time

G — E F G G F

G G G

G F G E G —

F F

F G E

G G G

E G G G E

E

Sensitivity

G F G G F F G

G E E

G F

E,G F,G — F

P P

F G G

E E G,E

E G G G E

E,G

N = No or None E = Excellent G = Good F = Fair

Orientation table for pressure detectors

Annex D of OMV Petrom S.A. Concept study – RO-EP-IN-TEN-001-01-E Edition 01 Valid from: 07/02/2012 Page 1 of 1

Table 1

Bello

ws

- A

bs.

Pre

ss. M

oti

on

Bala

nce

- A

bs.

Pre

ss.

Fo

rce B

ala

nce

- A

tm.

Pre

ss.

Ref.

Mo

tio

n B

al.

- A

tm.

Pre

ss.

Ref.

Fo

rce B

al.

- A

nero

id M

an

ost

ats

Bo

urd

on

-

C-B

ou

rdo

n

- S

pir

al B

ou

rdo

n

- H

elical B

ou

rdo

n

- Q

uart

z H

elix

Dia

ph

rag

m

- A

bs.

Pre

ss. M

oti

on

Bala

nce

- A

bs.

Pre

ss.

Fo

rce B

ala

nce

- A

tm.

Pre

ss.

Ref.

Mo

tio

n B

al.

- A

tm.

Pre

ss.

Ref.

Fo

rce B

al.

Ele

ctr

on

ic

- S

train

Gau

ge

- C

ap

acit

ive S

en

sors

-

Po

ten

tio

metr

ic

- R

eso

nan

t W

ire

- P

iezo

ele

ctr

ic

- M

ag

neti

c

- O

pti

cal

Hig

h p

ress

ure

sen

sors

-

Dead

Weig

ht

Pis

ton

Gau

ge

- B

ulk

Mo

du

lus

Cell

- M

an

gan

in C

ell

Man

om

ete

rs

- In

vert

ed

Bell

- R

ing

Bala

nce

- Flo

at

Man

om

ete

r -

Baro

mete

rs

- V

isu

al M

an

om

ete

rs

- M

icro

man

om

ete

rs

Pre

ssu

re r

ep

eate

rs

- D

/P C

ell

- S

td. D

iap

hra

gm

-

Bu

tto

n D

iap

hra

gm

Ion

izati

on

-

Ho

t C

ath

od

e

- C

old

Cath

od

e

Th

erm

al

- T

herm

oco

up

le

- T

herm

op

ile

- R

esi

stan

ce W

ire-P

iran

i -

Co

nvectr

on

Mech

an

ical

- Q

uart

z H

elix

- M

cLeo

d

- M

ole

cu

lar

Mo

men

tum

-

Cap

acit

an

ce

- S

pin

nin

g B

all

Inline device √ √ √ √ √

√ √ √ —

√ √ √ √

√ √ √ √ √ √ √

— √ —

√ √ √ √ √ —

√ √ √

— —

√ √ √ √

— √ √ √ √

Laboratory or pilot plant device

√ √ √ √ √

√ √ √ √

√ √ √ √

√ √ √ √ √ √ √

√ √ √

√ √ √ √ √ √

√ √ √

√ √

√ √ √ √

√ √ √ √ —

Local readout (gauge) √ — √ — —

√ √ √ √

√ — √ —

√ — — — — — —

√ — —

√ √ √ √ √ √

— — —

√ √

√ √ √ √

√ √ √ √ √

Remote readout transmitter

√ √ √ √ —

√ √ √ √

√ √ √ √

√ √ √ √ √ √ √

— √ √

√ √ √ — — —

√ √ √

√ √

√ √ √ √

— — — √ √

Table 2

Gen

era

l-p

urp

ose

B

ou

rdo

n-t

ub

e

ind

icato

r

Hig

h-a

ccu

racy t

est

g

au

ge

Bo

urd

on

/sp

iral

case

-mo

un

ted

in

dic

ato

r/re

co

rder

Sp

rin

g-a

nd

-bello

w

case

-mo

un

ted

re

co

rder

Nest

ed

cap

sula

r case

-mo

un

ted

re

co

rder

Lo

w-p

ress

ure

bell

case

-mo

un

ted

in

dic

ato

r

Beam

-mo

un

ted

st

rain

gau

ge

(sen

sor

on

ly)

4–20-

mA

DC

ou

tpu

t

Pie

zore

sist

ive

tran

sdu

cer

4–20-m

A D

C o

utp

ut

“S

mart

”

pie

zore

sist

ive

tran

smit

ter

4–20-m

A D

C o

utp

ut

“S

mart

” f

ield

co

mm

un

icato

r fo

r re

mo

te

calib

rati

on

an

d

co

nfi

gu

rin

g o

f “sm

art

”

tran

smit

ter

Cap

acit

ive

sen

sor/

tran

smit

ter

Range (bar or mmH2O)

1÷690[1] ~-1÷207[1] ~-1÷3,450[1] ~-1÷3,5[1] 0.7÷6.2[1] -3÷3[2] 0÷69[1] 0÷365[1] 0÷414[1] — 25[2] ÷414[1]

Accuracy (%) 2 0.1÷0.01 0.5 0.5 0.5 2 0.25 0.5 0.1 — 0.2

Cost ($) 100 300-6,000 1,200 1,600 1,600 2,200 800 500 1,200÷2,000 1,000÷3,000 1,000

[1] = bar [2] = mmH2O

Orientation table for density sensors

Annex E of OMV Petrom S.A. Concept study – RO-EP-IN-TEN-001-01-E Edition 01 Valid from: 07/02/2012 Page 1 of 2

Table 1: Liquid density sensor design

An

gu

lar

Po

siti

on

Typ

e

Ball T

yp

e

Cap

acit

an

ce T

yp

e

Dis

pla

cem

en

t T

yp

e

- B

uo

yan

t Fo

rce D

isp

lacer

- C

hain

Bala

nce F

loat

- E

lectr

om

ag

neti

c S

usp

en

sio

n

Hyd

rom

ete

rs

Hyd

rost

ati

c H

ead

Typ

e

Osc

illa

tin

g C

ori

olis

Rad

iati

on

Typ

e

So

nic

/Ult

raso

nic

Tw

in T

ub

e

Vib

rati

ng

Fo

rk T

yp

e

Vib

rati

ng

Pla

te T

yp

e (

als

o f

or

gase

s)

(cu

rren

tly n

ot

man

ufa

ctu

red

)

Vib

rati

ng

Sp

oo

l T

yp

e (

als

o f

or

gase

s)

Vib

rati

ng

U-T

ub

e T

yp

e

Weig

ht

of

Fix

ed

Vo

lum

e T

yp

e

Clean Process Streams √ √ √ √ √ √

√ √ √ √ √ √ √ √ √ √ √

Slurry Service — — √ — — —

— √ √ √ √ √ L L L — √

Ap

plicab

le t

o

Viscous or Polymer Streams

— — √ — — —

— √ √ √ √ — L L L — √

Minimum Span Based on Water SG=1.0

0.1 Digital 0.1 0.005 0.005 0.01

0.05 0.05 0.1 0.05 0.2 Digital 0.02 0.1 0.3 0.05 0.05

Accuracy in % of Span or SG Units

0.5 0.01 SG 1 1 1÷3

0.5÷1

1 0.2÷1 0.02 SG or better

1 1÷5 0.0001 0.001 SG 0.2 0.001 SG 0.00005÷0.005 SG 1

Design Pressure and Temperature Limitations (Bars/°C)

69/260 41/71 34.5/71 130/472 34/232 14/177

7/93 345/177 345/426 Unlimited 69/199 100/180 207/200 100/95 50/149 200/260 165/260

Temperature Compensation Available

N.S. N.S. √ N.S. √ √

√ N.S. √ √ √ √ √ — √ √ √

Direct Local Indicator — √ — — √ —

√ √ — — — √ — — — — √

Transmitter √ √ √ √ √ √

√ √ √ √ √ √ √ √ √ √ √

N.S. = Non-standard L = Limited

Orientation table for density sensors

Annex E of OMV Petrom S.A. Concept study – RO-EP-IN-TEN-001-01-E Edition 01 Valid from: 07/02/2012 Page 2 of 2

Table 2: Gas density sensor design

Sensors Operating at Actual Flowing Conditions - Centrifugal Type - Displacement Type - Fluid Dynamic Type

Specific Gravity Detectors Operating at Near-Ambient Conditions - Electromagnetic Suspension Type - Gas Column Balance Type - Manual Displacement Type Elements - Thermal Type - Viscous Drag Type

Minimum span (kg/m3) 16 16 8

(Minimum Span Based on Air SG = 1.0) 0.01 SG 0.1 SG 0.1 SG 0.5 SG 0.1 SG

Inaccuracy in % of Span or in SG Units 0.1÷0.5 0.25

2

0.0001 SG 0.001 SG 0.002 SG 0.01 SG

0.001÷0.002 SG

Design Pressure and Temperature Limitations (Bars/°C) 138/49 103/93 3.5/232

ATM/49 1.4/60

ATM/49 ATM/49 ATM/49

Manually Operated Indicator — √ √

— — — √ —

Continuous Indicator √ √ √

— √ √ — √

Transmitter √ √ √

√ √ — √ √

Orientation tables for safety and miscellaneous sensors

Annex F of OMV Petrom S.A. Concept study – RO-EP-IN-TEN-001-01-E Edition 01 Valid from: 07/02/2012 Page 1 of 9

Table 1: Electrical meters and sensors AMMETERS AC AMMETERS DC VOLTMETERS AC VOLTMETERS DC WATTMETERS AC WATTMETERS DC

Meter Types and Accessories:

Rectifier Moving iron vane Moving iron vane with transformer Digital Digital with Transformer/ Hall effect probe

Permanent magnet moving coil Permanent magnet moving coil with shunt Digital Digital with current probe

Rectifier Moving iron vane Moving iron vane with transformer Electrostatic Digital

Permanent magnet moving coil Permanent magnet moving coil with resistor Digital

A. Single-phase 1-element electrodynamic Digital 1-element electrodynamic with transformer B. Three phase 2-element electrodynamic with transformer 2.5-element electrodynamic with transformer Digital

1-element electrodynamic Digital

Full-Scale Meter Range (A, V, W)

0.5÷20 x 10-3 A 1÷50 A 10-8,000 A 200 x 10-6÷10 A 2÷1,000 A

0.02 x 10-3÷50 A 20÷20,000 A 200 x 10-6÷10 A 2÷1,000 A

3÷800 V 3÷600 V 150÷18,000 V 10÷1,000 V 100 x 10-3÷750 V

1÷600 V 250÷30,000 V 100 x 10-3÷750 V

A. 125÷1,000 W 2 x 10-3÷15,000 W 1,000÷100 x 106 W B. 1,000÷100 x 106 W 1 x 104÷1 x 108 W 2 x 10-3÷15,000 W

100÷2,000 W 2 x 10-3÷15,000 W

Recommended Applications

Low range, high frequency General use up to 750 V High range, over 750 V, long meter leads General use, medium frequency High range, medium frequency

General use High range General use High range

Low range, high frequency General use High range, circuit isolation High range General use, medium frequency

General use High range, high sensitivity General use

A. Low power, single phase 2-wire circuits General use, single phase 2-wire circuits General use, single phase circuits B. General use, three phase, there wire General use, three phase, four wire General use, three phase, three or four wire

General use, low power General use

Accuracy 3% of full scale 0.5÷2% of full scale 0.5÷2% of full scale ppm÷2% of full scale ppm÷2% of full scale + 0.6÷1.2% of secondary rating

0.3÷2% of full scale 3% of full scale ppm÷2% of full scale ppm÷2% of full scale + 0.25% of shunt rating

3% of full scale 0.5÷2% of full scale 0.5÷2% of full scale 0.5÷2% of full scale ppm÷2% of full scale

0.3÷2% of full scale 0.3÷2% of full scale ppm÷2% of full scale

0.5÷2% of full scale (non-digital) ppm÷2% of full scale (digital)

0.5÷2% of full scale ppm÷2% of full scale

Costs ($) 150 50 50÷100 100÷2,000 100÷2,000

50 150 50 50

150 50 50÷100 500 50

50 50 50

500 (non-digital) 50 (digital)

500 50

A = Amper V = Volt W = Watt



Table 2: Energy management devices (peak load shedding) Electromechanical Electronic Digital

Energy Saving Potential Up to 25% of utility bill Up to 25% of utility bill Up to 25% of utility bill

Number of Controllable Under 10 Up to 16 Practically unlimited

Costs ($) 500÷1,000 1,000÷10,000 up to 25,000

Table 3: Excess Flow and Regular Check Valves Check valves that prevent flow reversal Excess flow check valves that shut off the forward flow in case of

high flows caused by pipe rupture

Size (mm) 25÷1820 12÷250

Materials of Construction Cast iron, Bronze Steel 304 stainless steel 316 stainless steel Polyvinyl chloride Polypropylene Polyvinylidene fluoride Chlorinated polyvinyl chloride

Cast iron, Bronze Steel 304 stainless steel 316 stainless steel Polyvinyl chloride Polypropylene Polyvinylidene fluoride Chlorinated polyvinyl chloride

Costs ($) — —

800 (for a 75 mm excess flow check valve in cast iron or brass) 2,000 (for a 75 mm excess flow check valve in steel)

mm = millimetre



Table 4: Flame, Fire, and Smoke Detectors Flame (pilot and main flame detectors in combustion processes) Fire (fire safety devices) Smoke (detect smoldering

and the incipient of fires)

Type 1. Heat Sensors 2. Rectification 2.1. Rectifying Flame Rod 2.2. Visible Light Rectifying Photo Tube 3. Radiation 3.1 Infrared Radiation (Lead-Sulfide Photocell ) 3.2. Visible Radiation (Cadmium-Sulfide Photocell) 3.3. Ultraviolet Radiation (Ultraviolet Detector Tube)

1. Thermal Sensors 1.1 Rate-of-rise sensor 1.2 Absolute temperature sensor 2. Optical Flame Sensors 2.1. Ultraviolet 2.2. Infrared 2.3. Ultraviolet / Infrared 2.4. Dual Infrared 2.5. Multi- Infrared 2.6. Closed Circuit Television

Ionization Chamber Sensors Photoelectric Sensors

Typical Optical Flame Detection Distances (Feet) NR = no response

—

2. Optical Flame Sensors

UV IR Dual IR UV/IR Multi-IR

Gasoline 90 85 100 100 210

Diesel 65 65 50 40 150 Methanol 50 50 20 55 150

Methane 80 45 25 90 100

Hydrogen 50 NR 15 NR NR

Metal fires

15 NR 15 NR NR

Black powder

15 40 40 NR NR

—

False Alarm Source Impact N.E. = No effect S.E. = Some effect Sv.E. = Severe effect

—

2. Optical Flame Sensors

UV IR Dual IR UV/IR Multi-IR

Arc welding Sv.E. S.E. S.E. S.E. S.E.

Modulated IR radiation

N.E. S.E. S.E. N.E. N.E.

Electrical arcs Sv.E. S.E. N.E. N.E. N.E.

Radiation (nuclear)

Sv.E. N.E. N.E. N.E. N.E.

Lightning Sv.E. N.E. N.E. N.E. N.E.

Grinding (metal)


Artificial lighting


Sunlight S.E. N.E. N.E. N.E. N.E.

—

Comparison of Flame Safeguards RFR = Rectifying Flame Rod VLRPT = Visible Light Rectifying Photo Tube IR = Infrared Radiation VL = Visible Radiation UV = Ultraviolet Radiation

Advantages RFR VLRPT IR VL UV

Same detector for gas or oil flame — — √ — √

Can pinpoint flame in three dimensions √ — — — —

Viewing angle can be orificed to pinpoint flame in two dimensions — √ √ √ √

Not affected by hot refractory √ — — √ √

Checks own components prior to each start √ √ √ √ √

Can use ordinary thermoplastic covered wire for general applications, no shielding needed √ √ — — √

No installation problem because of size — — √ √ —

Disadvantages RFR VLRPT IR VL UV Difficult to sight at best ignition point — — √ — —

Exposure to hot refractory may reduce sensitivity to flame flicker and require orificing — — √ — —

Flame rod subject to rapid deterioration and warping under high temperatures √ — — — —

Not sensitive to extremely hot premixed gas flame — — √ √ —

Temperature limit too low for some applications √ √ √ √ —

Shimmering of hot gases in front of hot refractory may simulate flame — — √ — —

Hot refractory background may cause flame simulation — √ — — —

Electric ignition spark may simulate flame — — — — √

—

—

Costs ($) 500 (Flame rod or thermocouple type 800÷3,000 (Optical flame type)

10 (household)

100 (addressable, IS)



Table 5: Leak Detectors Above ground detectors

1. Pressurization 2. Bubbles, paints, etc. 3. Combustible and toxic 4. Ultrasonic 5. Thermal conductivity 6. Halogen leak detectors 7. Others (vacuum, thermograph, etc.)

Underground leak detectors 1. Level Monitoring 1.1. Thermal dispersion 1.2. Thermal conductivity 2. Soil Detectors 2.1. Passive in-ground sensor (Van der Wall) 2.2. Aspirated sensor 2.3. Standpipe detector

Sensitivity*/ Accuracy** 1. —

2. 10-4 cm3/s*

3. Pocket-Sized, Portable Toxic Gas Monitors

Alarm Setpoint (ppm)

Accuracy**

CO 200 ±10 ppm FS; ±5 ppm in 0 to 200 range

H2S 50 ±10 ppm FS; ±3 ppm in 0 to 100 range

SO2 20 ±10 ppm FS; ±3 ppm in 0 to 100 range

NOx 200 ±10 ppm FS; ±5 ppm in 0 to 200 range

NO2 20 ±2 ppm FS

4. —

5. 10-5 cm3/s*

6. 10-7 cm3/s* 7. —

Portable Combustible Gas Detectors

Compounds Formula Sensitivity (ppm)*

Acetylene C2H2 50

Alcohols R—OH 50

Hydrogen sulfide H2S 5

Gasoline — 1

Sulfur dioxide SO2 5

Vinyl chloride C2H3Cl 5

Liquid hydrocarbons — 50

Costs ($) 1. — 2. 40 (a case of bubbling foam bottles) 3. 300 (a portable, intrinsically safe combustible gas detector with 100 ppm sensitivity) and 600 (a portable toxic gas monitor) 4. 1,200 5. 1,600 (a portable detector with 10-5 cm3/s sensitivity) 6. 3,000 7. 3,000÷150,000; around 10,000 (thermography sensors) and 25,000 (average mass spectrometer)

1. — 2. 2,500 (single-point gas monitoring applications) and 8,000 (up to 12 points gas monitoring applications)

Application

Application Detector Options

Personnel protection Gas badges

Gas leaks, general Handheld gas detectors Personnel protection indicators Wall mounted gas detector

Water leaks Colormetrics Tracer dyes

Small parts Immersit immersion fluid Tracer dyes

Unpressurized pipes and containers

Colormetrics Ultrasonic leak detector Tracer dyes

Pressurized pipes and containers

Liquid leak detector Ultrasonic leak detector

Large parts Liquid leak detector

Large containers Hydrostatic leak testing Immersit immersion fluid Handheld gas detectors Ultrasonic leak detector Colormetrics Tracer dyes Inspection penetrants

Oil/fuel leaks Colormetrics Tracer dyes FuelGuard for AFVs



Table 6: Linear and Angular Position Detection Technology Potentiometer Linear variable differential transformer Magnetostrictive Hall-effect Encoder

Linear/Rotary Rotary (Linear) Linear (Rotary) Rotary Linear Rotary (Linear)

Linearity (%) 0.25 0.25 0.05 1 0.025

Noncontact No Yes Yes Yes Yes

Costs ($) 10 (potentiometer) 550 (smart transmitter) 600 (Fieldbus transmitter)

1,600 400 650 (smart transmitter) 700 (Fieldbus transmitter)

500

Table 7: Metal Detectors

Technology Electro-magnetic

Type 1. Transmit-receive detector (T/R) 2. Beat frequency oscillator (BFO)

Capability of hand-held metal detector

1. Transmit-receive Transmit-receive, very low frequency

Medium Air Water Sand Air Water Sand

Object dime dime dime dime dime dime Detection range Distance (cm) 7.5÷15 10÷17.5 15÷17.5 15÷20 15÷20 15÷17.5

2. Beat frequency oscillator

Medium Air Water Sand

Object dime dime dime Detection range

Distance (cm) 15÷17.5 15÷17.5 15÷17.5

Applications Products in liquid, paste, or solid form on conveyors, in ducts, or in pipes can be monitored for the presence of metal objects. Units are also available to detect the location of underground pipes and cables, or for “beachcombing” for coins or jewelry.

Operating Temperature -40÷49°C

Operating Pressure Atmospheric or vacuum

Materials of Construction Search head and electronics are housed in aluminum, plastic, or stainless steel

Search Head Window Sizes Highly variable. Typical belt detector window sizes range from 2.5x61÷30x61 cm

Range of Detection 2.5÷25 cm for both ferrous and nonferrous metals. The smaller the search head window size and the shorter the range, the better will be the sensitivity.

Sensitivity The smallest diameter sphere of ferrous and nonferrous metals that can be detected is about 1 mm. Distance from the search coil to the object is in direct proportion to the size of the object.

Costs ($) - start at 100 (proximity limit switches) - 2,500 or more (search coils or search heads installed on belts and provided with interlocks for flap ejectors)

Table 8: Noise sensors

Principle Inductive Dynamic Electrostatic Piezoelectric (or electrostrictive) Resistance variation

Applications 1. Noise/sound level measurement for Occupational Safety and Health Administration (OSHA) and Department of Transportation (DOT) compliance 2. Sound spectrum and acoustic emission analysis for non-destructive testing and safety applications

Air Microphones

Type of Microphone Frequency Response Range, Hz

Output, dB* Typical Characteristics Typical Use

Carbon Telefone transmitter 300÷4,000 (useful range) –25÷–45 Inexpensive, with high output in the speech frequency range Telephone Capacitor microphone 12÷15,000 –48 Extremely stable, wide, and flat frequency response Measurement of sound level

Carrier-type capacitor microphone 0.1÷20,000 Depends on auxiliary unit Widest possible frequency response; uses auxiliary electronics, with any of several microphone units

Measurement of sound in extreme conditions

Crystal microphone 30÷12,000 –65 Good frequency response, usually semicardioid pattern; often temperature sensitive Public address, recording

Cardioid microphone 20÷12,000 –80 Good frequency response, cardioid or “unidirectional” pattern Public address, recording, etc.

Ribbon microphone 20÷15,000 –85 Good frequency response; can be used either as pressure or velocity type Live performance, recording

Wave microphone 80÷8,000 –80 Can be highly directional, because of construction Broadcasting, special use

Designs/ Performances

Water Hydrophones

Ranges 30÷140 dB

Frequencies Usually from 20 to 20,000 Hz; special devices can be used to measure from 0.1 to 40,000 Hz

Accuracy Generally ±2 dB for OSHA and DOT compliance; up to ±0.5 dB in special designs

Operating Temperature and Relative Humidity

Generally from -9÷65°C) at up to 95% relative humidity

Weighing of Sound Curve “A”: approximates the human ear; Curve “B”: combined high- and mid frequency decibels; Curve “C”: read all frequencies but gives better response at lower frequencies

Costs ($) 25 (Hearing protector ear muffs) 200 (Acoustical calibrators) 700 (a battery-operated sound level meter operating with “A” weighing and provided with acoustical calibrator) 900 (a battery-operated sound level meter operating with “A, B, C” weighing and provided with acoustical calibrator) up to 100,000 (computerized installations of acoustic emission analyzers for non-destructive testing using piezoelectric sensors)



Table 9: Proximity sensors and limit switches

Types Capacitance Inductive Optical, photoelectric, or fiber-optic Pneumatic and air gauging Ultrasonic

Switch Dimensional or thickness sensor

Inductive Magnetic, which includes the Hall effect, the variable reluctance, and the magnetically actuated reed switch types

Linear variable differential transformer (LVDT) and variable resistor

Mechanical and electromechanical limit switches

Switch Laser-based distance, dimension, or thickness sensor

Air gap sensors

Dimension sensors

Echo-type switch Displacement transducer

Operating Temperatures

Typically from -46 to 66C. The temperature range of high-precision devices can be more restricted, while specialized sensors can take wider ranges. Mechanical limit switches operate from -32 to 121°C

Objects detected Metallic and nonmetallic Metallic, ferrous, or nonferrous Metallic and nonmetallic

Metallic and nonmetallic

Opaque or reflective; fiber-optic version can detect objects under 0.1 mm diameter

Metallic and nonmetallic Metallic and nonmetallic

Detection Ranges 3÷25 mm 2÷50 mm Wide Physical contact Up to 60 m Microinches to inches 50 mm÷30 m Costs ($) — — — — 200÷1,200 — — >3,000 (resolution

of 1μm) 20 — 300÷600 <1,000÷3,000

Table 10: Relief valves Type of design Spring loaded Weight-loaded Balanced by bellows seals Pilot-operated

Design Pressure Ranges Screwed designs from 34 kPa to 69 MPa, higher as special Flanged steel designs, ANSI CL 150#, 300#, 600#, 900#, 1500# and 2500# ASA Flanged cast iron units in 125# and 250#

Vacuum: –43.2 mm H2O to –96.5 kPa Low pressure: 76.2 mm H2O to 1034 kPa Medium to high pressure: 0.345 to 42.75 MPa

Design Temperature –268 to 538°C with suitable material selections for pressure parts, trim, and springs; breaks occur in the temperature ratings at 232°C and 427°C

Inlet Connection Sizes 12.5÷150 mm; some suppliers up 300 mm for special services 25÷250 mm with double outlets starting at 50 mm

Orifice Areas: API designated orifices: D (0.11 in2), E (0.196 in2), F (0.307 in2), G (0.503 in2), H (0.785 in2), J (1.287 in2), K (1.838 in2), L (2.853 in2), M (3.6 in2), N (4.34 in2), P (6.38 in2), Q (11.05 in2), R (16.0 in2), and T (26.0 in2) Non-API orifices and full-bore orifices are available in areas up to 84 in2

Materials of Construction Pressure parts: cast iron, bronze, cast steel, 300 and 400 series stainless, nickel steel, Monel, Hastelloy, high-temperature carbon steel alloys, materials in compliance with NACE MR0175; trim: basically any machinable alloy, can be cryogenic, NACE, or high-temperature trim

Seat and Seal Materials: Metal to metal or soft seats Soft seat material options include Aflas, Buna-N, ethylene propylene, Kalrez, Peek, Teflon, Urathene, Viton, etc.

Accessories Backflow preventer, dual pilots, field test connection with indicator, filter, pilot lift lever, pressure spike snubber, remote blowdown, remote pressure sensor, remote valve lift indicator, valve monitor, valve position indicator

Cost

Accuracy ±2 PSI for pressures up to and including 483 kPag

±3% for pressures above 483 to 2068 kPag ±2% for pressures from 2068 to 9997 kPag ±1.5% for pressures above 9997 kPag



Table 11: Rupture discs

Types Forward Acting Reverse Acting

Characteristic Prebulged (FAB Composite (FAC) Scored (FAS) Flat Graphite Knife (RAK) Scored (RAS)

Sizes (mm) 4.8÷1,120

Burst Pressure Ranges (barg) 0.017÷8274

Maximum Operating Pressure 50 to 90% of marked burst pressure depending on design

Rupture Tolerance ±5% for B.P.>2.75 barg and ±1.04 bars for B.P.<=2.75 barg

Cost Low Medium High Medium Medium Medium High

Max operating ratio (%) 70 80 90 50 80 90 90

Life under cyclic conditions @ max operating ratio High Low Medium Low Medium High High

Fragmenting Yes Varies No No Yes No No

Vacuum resistant With support With support Yes With support With support Yes Yes

Low pressure Yes Yes Yes Yes Yes Yes Yes

High pressure Yes No Yes No No No Yes

Table 12: Tachometers and angular speed detectors

Types Impulse tachometers Optical encoders and photoelectric sensors Stroboscopes AC and DC tachometers Induction sensors Magnetic sensors Pneumatic sensors

Range Up to 999,990 rpm

Acuracy Generally 0.01% of reading, or 1 rpm up to a reading of 100,000 rpm

Operating temperature Up to 93°C

Costs ($) For angular position sensors see Table 6

For proximity switches see Table 9

150 (hand-held mechanical tachometers)

250 (microprocessor-based handheld contact or noncontact type tachometers)

500 (handheld stroboscopes with internal batteries with analog displays) and 750 (with digital displays)

600 (a microprocessor-based programmable display for panel-mounted installations); 150 (the associated optical sensor), 150 (the associated proximity, or magnetic sensor)

700 (a magnetic wheel sensor and signal conditioner for an analog transmitted signal)

Note: Most angular position sensors mentioned in Table 6 and proximity sensors mentioned in Table 9 can be also configured as tachometers.

Table 13: Thickness and Dimension Measurement Types Capacitance Inductive,

magnetostrictive, and Hall-effect

Linear variable differential transformer

Mechanical micrometers Laser Pneumatic Ultrasonic Radiation (Beta or x-ray) Optical Micrometer

Thin-Film Deposition and Coating Interferometer

Ranges 3÷25 mm 2÷50 mm From 0.025 mm up

Up to 25 mm Wide, can be 0.1 to 8 mm Microinches to inches

0.25÷250 mm From 0.0064 mm in plastics to 51 mm in steel

10÷200 μm 15 nm÷50μm

Accuracy Generally ±1% of measured value 0.01 mm and resolution 0.001 mm

0.0025 mm with laser gauging and one millionth of a millimetre with laser interferometers

Generally ±1% of measured value

±1% of measured thickness ±1% of basic weight measured or ±0.25% of thickness measured

0.25μm 1% of reading

Costs ($) 2,000÷5,000 2,000÷5,000 500 (a contacting linear gauge with digital readout) 300÷1,000 (a gauge stand) 2,000 (a linear gauge with digital-analog output)

>10,000 — 500 (a contacting linear gauge with digital readout) 300÷1,000 (a gauge stand) 2,000 (a linear gauge with digital-analog output)

>5,000 2,000÷5,000 2,000÷5,000

Sensitivity 0.001 inch — 20μinch 0.0001 inch 0.05 inch — 0.01 inch 50 mg/cm2(Actual sensitivity depends on the specified value for a given instrument divided by its density (g/cm3)

0.1μm 1% of reading

Applications* Note * = Whether a device is suitable for continuous process instrumentation is indicated by N (no) or Y (yes).

Insulating sheets, films (Y)

— Low-speed continuous foils, web, sheet, film materials, calibration, sampling (Y)

Sampling, quality control, calibration, foils, web, sheet, film materials (N)

Mounted directly on production line and is used to alarm on any out-of-tolerance condition (Y)

— Rigid, relatively thick sheets, or pipe walls accessible from one side only (Y)

Metal foils and plastic films (Y)

Provides thickness monitoring for silicone wafers (Y)

Measures thin-film deposition layer thickness and uniformity of semiconductors and dielectric layers (Y)



Table 14a: Force transducers Table 14b: Torque transducers

Hand-held or portable force gauge Load cell Types

Mechanical Digital

Mechanical Dynamometers Piezoelectric Dynamometers

Operating Temperature -50÷150°C

Ranges 0÷0.5 to 0÷220,000 kg 0.5÷5,000,000 kg

Accuracy (of full scale) 0.2÷0.5% 0.02%

Costs ($) 500÷750 (mechanical force gauge) 500÷2,000 (digital force gauge) 1,000÷3,000 (motorized test stands for manual operation) 7,000 (programmable, computer-compatible unit)

50÷500 (single beam load cells) 500÷1,000 (standard load cells) 2,000 (a single-component quartz force sensor) 5,000÷7,000 (digital dynamometer controller)

Note: For a detailed view, please see Table 16 (weight sensors)

Table 15: Vibration, shock, and acceleration Types Seismic (Inertial)

sensors Piezoelectric sensors Piezoresistive and

strain gages Electromechanical sensors

Capacitive and electrostatic sensors

Micro- and nanosensors

Velocity sensors Noncontact proximity sensors

Mechanical switches Optical sensors

Operating Temperature -20÷70ºC Generally -50÷260ºC Special designs available for -268÷816ºC

-40÷121ºC — — -40÷120ºC — — — —

Typical Range of Vibration Frequency (Hz)

DC÷50 Hz 1÷15,000 Hz <1÷30,000 Hz (special designs)

0÷1000 Hz 10÷1000 Hz — 0÷3500 Hz — 0÷5000 Hz — —

Typical Range of Vibration Amplitude (g)

±0.5 or ±2.0 g <1÷1000 g (generally) > 10,000 g (special sensors)

— 0.5÷254 mm/s — ±5,000 g — 2÷600 g (capacitance) 5÷160 mil (eddy current)

— —

Nonlinearity — 1% of straight line 1% — — — — — — —

Sensitivity 0.02 g/g ~1000 mV/g (amplitude ranges up to 5 g) ~3 mV/g or 5 pico C/g (ranges around 1000 g)

0.25÷25 mV/g (for ranges of 5÷1000 g)

250 mV/in./s — 0.05 mV/g — — — —

Rotating transducer Stationary transducer Reaction torque transducer Type

Direct Contact (Slip-rings and brushes)

Inductive Coupling (Rotating transformer)

Magnetostrictive Torque Transducer

Angular Displacement Type Torque Transducers

Operating Temperature

-50÷150°C

Torque ranges

Up to 60 kg-cm (torsion bar type indicators) Up to 500,000 kg-cm (stationary and rotary strain gauge type torque sensor) Up to 1.,700,000 kg-cm (reaction torque sensor)

RPM ranges 2,500÷6,000 Up to 15,000 — — —

Accuracy (of full scale)

3% (torsion bar monitors) 0.1% (stationary and rotary strain gauge sensor nonrepeatability, nonlinearity, and hysteresis)

Costs ($) 1,000 (electronic digital torque gauges) 1,500÷2,000 (stationary torque sensors for ranges 115÷11,500kg-cm) 2,500÷4,000 (rotary sensors for ranges 115÷11,500kg-cm) 2,000 (slip-ring assembly)

1,000÷2,500 (reaction torque sensors for ranges 115÷11,500kg-cm) 5,000 (reaction torque sensors for ranges up to 100,000 lb-in) 8,000 (reaction torque sensors for ranges up to 200,000 lb-in) 15,000 (reaction torque sensors for ranges up to 500,000 lb-in) 18,000 (reaction torque sensors for ranges up to 1,500,000 lb-in)



Table 16: Weight sensors Mechanical (lever, spring) Mechanical cell Electronic load cells Feeders

(screw, belt, gravimetric, nuclear, and loss-in-weight

Types

Laboratory Industrial Hydraulic load cells

Pneumatic load cells

Strain gauge 1. Bending beam 2. Shear beam 3. Canister 4. Ring and pancake 5. Button and washer

Piezoelectric Piezoresistive (semiconductor)

Capacitance Inductive Reluctance Magnetostrictive Nuclear

Operating Temperature Ranges

Ambient -23÷57°C -18÷52°C -18÷52°C -20÷70°C (normally) -20÷230°C (special units)

—

Ranges From 0÷3 g to 0÷150 kg

From 0÷0.5 to 450,000 kg

45÷450,000 kg) 4.5÷4500 kg From 0÷5 to 0÷4,500,000 kg 1. 10÷5,000 lb 2. 10÷5,000 lb 3. to 500,000 lb 4. 5÷500,000 lb 5. 0÷50,000 lb (0÷200 lb typical)

From 0÷5 to 0÷4,500,000 kg 1. 0–40,000 lb (Helical) 2. Fiber optic 3. Piezoresistive

—

Accuracy 0.1µg (readability for 0÷3g range) 50g (readability for 0÷150kg)

±0.01÷±0.1% of full scale

±0.1%÷±1% of full scale

±0.1%÷±1% of full scale

0.03÷0.25% of full scale 1. 0.03% 2. 0.03% 3. 0.05% 4. — 5. 1%

0.03÷0.25% of full scale 1. 0.2% 2. 0.1% 3. 0.03%

—

Applications — — Tanks, bins, and hoppers; hazardous areas

Food industry; hazardous areas

1. Tanks; platform scales 2. Tanks, platform scales, off-centre loads 3. Truck, tank, track, hopper scales 4. Tanks, bins, scales 5. Small scales

1. Platform, forklift, wheel load, automotive seat weight 2. Electrical transmission cables; stud or bolt mounts 3. —

—

Advantages — — Takes high impacts; insensitive to temperature

Intrinsically safe; contains no fluids

1. Low cost, simple construction 2. High side load rejection, better sealing and protection 3. Handles load movements 4. All stainless steel 5. Small, inexpensive

1. Handles off-axis loads, overloads, shocks 2. Immune to RFI/EMI and high temps; intrinsically safe 3. Extremely sensitive; high signal output level

—

Disadvantages — — Expensive, complex

Slow response; requires clean, dry air

1. Strain gages are exposed, require protection 2. — 3. No horizontal load protection 4. No load movement allowed 5. Loads must be centred; no load movement permitted

1. — 2. — 3. High cost; nonlinear output

—

Overload Limitations

— — — — Up to 125% of rating including shock, impact, or static loading —

Nonrepeatability — — — — 0.01÷1% (generally) —

Nonlinearity — — — — 0.03÷2% (generally) —

Hysteresis — — — — 0.02÷2% (generally) —

Output Signals — — — — 2÷3 mV per volt of excitation. Excitation voltage is usually around 10 V. —

Design Materials — — — — For high capacities, the load (spring) elements are usually steel alloys, while for low capacities, aluminum alloys are used. The strain sensing grid can be constantan, Karma, Isoelastic, or platinum tungsten. The strain gauge backings include polyamides, epoxies, or reinforced epoxies. The bonding adhesive is often cyanoacrylate.

—

Orientation tables for analytical instrumentation

Annex G of OMV Petrom S.A. Concept study – RO-EP-IN-TEN-001-01-E Edition 01 Valid from: 07/02/2012 Page 1 of 42

Table 1: Analyzer Sampling: Process Samples Sample transport methods Single-Line Transport Bypass-stream transport Bypass-return fast loop

Applications Gas Sampling Probes Stack Gas Sampling (Automatic Stack Sampling) Automatic Liquid Samplers (Sampling of High-Pressure Condensate, Chemical Reactor Samplers, Duckbill Samplers) Solids Sampling Sampling Difficult Processes (Trace Analysis Sampling, Multistream Switching)

Components of Sampling Systems

Gas and liquid filters Bypass filters Liquid homogenizers Liquid grab sample collectors Chemical reactor sampling systems Solids samplers

Filter design Coalescing Gas Filter (Separating Liquids from Gases) Spargers, Packed Towers, and Strippers (removal of corrosive gases or condensable vapors from the sample) Coalescing Liquid Filter (Separating Two Liquid Phases) Entrained Gas Separator (Removing Gas Bubbles from Liquids) Slipstream and Bypass Filters Self-Cleaning and Rotary Disc Filters

Sample Conditioning Vaporizing Samples Entrainment Removal

Costs ($) 60 (compressed air filter) 300÷600 (stainless steel bypass filters ) 3,000 (continuous-flow ultrasonic homogenizers) 600 (sludge centrifuge) 750 (interval sampling pump only) 1500 and up (automatic liquid sampler system) 3,000÷6,000 (complete sampling system for single-process gas stream) 3,500÷7,000 (complete sampling system for single-process liquid stream) Note: The per-stream cost in a multistream sampling system drops as the number of streams increase.

Table 2: Analyzer Sampling: Stack Particulates Types of Sample Gas-containing particulates

Standard Design Pressure Generally atmospheric or near atmospheric

Standard Design Temperature -32 to 815°C

Sample Velocity 120÷3000 m per min

Materials of Construction 316 or 304 stainless steel for pitot tubes 316 or 304 stainless, quartz, or Incoloy for sample probes

Costs ($) 1300÷2500 (Probes only in 1÷3m) lengths with glass, quartz, or stainless steel lining 10,000÷15,000 for a complete EPA particulate sampling system (Reference Method 5)

Table 3: Analyzers Operating on Electrochemical Principles Voltametric Methods Potentiometry Polarography Galvanometry (Stripping) Amperometry Coulometry (controlled potential)

Standard Differential pulse polarography

Measured Variables Voltage Current, applied potential Current, applied potential Current, applied potential Current, time, concentration Integral of current as function of time

On-Line Instrument Yes Yes No No Yes Yes

Determinations pH Anions (F–,S–,Cl–) Cations (NH4+,Ca++,Mg++)

Pesticides Mercaptans Thiosulfates Chlorinated organics Toxic heavy metals

Aromatic hydrocarbons Aromatic amines Phenol Ammonium salts Carboxylic anhydrides N-nitrosamines

Heavy metals Selenides Halogens Thioamides Trace metals

Sulfates Halides Phenols Aromatic amines Olefins

Precious metals Alloys Dissolved oxygen

Accuracy: Generally 1% of full scale with absolute error values down to under 1.0 parts per billion (ppb)

Costs ($) 8,000 (Amperometric or polarographic residual chlorine transmitters) + 3,000 (the yearly cost of chemicals for the amperometric units (somewhat less for polarographic)) 2,500 (An electrochemical gas diffusion detector for hydrogen sulphide) 500 (Potentiometric probes for pH, oxidation–reduction potential, and ion-selective measurements) + 2,500 (associated transmitter) 7,000 (Electrochemical probes for nitrogen oxide detection in stacks) 3,500 (The electrolytic dissolved oxygen probe and transmitter) 4000÷8000 (Amperometric gas and dissolved ozone detector) 12,000÷20,000 (An electrochemical membrane diffusion system to automatically monitor toxic gas concentration in 16 locations).



Table 4: Biometers Method of Detection Photometric measurement of light emitted by chemical reaction

Sample Pressure Atmospheric

Sample Temperature Ambient

Sample Type Grab sample

Materials of Construction Glass

Range 10–7

÷10–2

μg of ATP per 10 ml sample of bacterial extract. Sensitively to 10−7

μg per 10 μl sample. It can be calibrated for number of bacteria per microgram of ATP.

Response Laboratory method: minutes after starting reaction

Cost ($) About 10,000

Note: ATP = Adenosine triphosphate Table 5: Biological Oxygen Demand, Chemical Oxygen Demand, and Total Oxygen Demand Types of Measurements Biological oxygen demand

(BOD) Chemical oxygen demand (COD)

Total oxygen demand (TOD)

Sampling Technique Depending on the application, composite flow-averaged or time-averaged samples are often automatically collected for manual introduction to an instrument, in addition to traditional instantaneous grab samples. Continuous-flow automatic sampling is common for instruments that are in continuous operation for process monitoring and control.

Sample Pressure Typically collected at near atmospheric pressure

Sample Temperature Collected at process or ambient conditions

Suspended Solids Varies with the application and instrument. Many applications are interested in the oxygen demand/impact of both the liquid and solids in the sample stream.

Materials of Construction Glass, quartz, Teflon, polyethylene, Tygon, polyvinyl chloride (PVC), stainless steel, ceramic

Ranges 0.1÷1500 mg/l is typical and higher with dilution

5÷1500 mg/l is typical and higher with dilution or some methods

0÷60,000 ppm

Accuracy 3÷20% 2÷10% 2÷5%

Response 3 min÷5 days 2÷15 min 3÷10 min

Costs ($) 500÷20,000 8,000÷20,000 5,000÷20,000

Applications (Purpose) Measurements of pollution load Measurements of pollution load Waste treatment plant influent (Determines loading of plant) Primary, secondary, and plant effluents (Determines efficiency of treatment and TOD load on the receiving waterway Enforcement programs (Determines pollution levels) Industrial process control (Determines process efficiency and leaks by continuous monitoring) Research and development (Evaluates waste treatment processes) Stream surveillance (Monitors fresh, estuarine, and marine water quality) Municipal or industrial water treatment plants (Monitors quality of influent water prior to treatment) Boiler feed and high-purity water monitoring (Measures TOD with great sensitivity)



Table 6a: Calorimeters Type of Designs A. Direct measurement by burning of fuel gas B. Inferential by calculation from composition and physical

analysis, including chromatography, mass spectrometry, etc C. Special designs such as reaction calorimeters of Mettler-Toledo, designs for the measurement of partial molar heat capacities of biopolymers by CSC, and total absorption calorimeters made by Opal

Applications 1. Custody transfer 2. Process monitoring and control 3. Blending and mixing of fuel gases 4. Gas and liquefied natural gas (LNG) processing 5. Compliance recording

Operation a. Continuous b. Cyclic c. Portable

Performance (1) Controlled environment (2) Varying ambient (3) High speed of response (4) Accuracy ±0.5% of full scale or better (5) Accuracy ±1.0% of full scale or better (6) Accuracy ±2.0% of full scale or better

Area Classification (a) General purpose (b) Explosion-proof

Cost ($) Under 10,000 [A, 2/3, a, (3)/(5)/(6)] 10,000÷15,000 [A, 2, a, (3)/(5)/(6), (b)] 15,000÷30,000 [A/B, 2/3, a/b, (1)/(2)/(4), (a)/(b)]

Table 6b: Calorimeter Features and Specifications

Type Application Operation Performance

Area Class

Type Dir

ect

Infe

ren

tial

Gen

era

l P

urp

ose

Ex-P

roo

f

Cu

sto

dy t

ran

sfe

r

Pro

cess m

on

ito

rin

g a

nd

co

ntr

ol

Ble

nd

ing

an

d m

ixin

g o

f fu

el g

ases

Gas a

nd

liq

uefi

ed

natu

ral

gas (

LN

G)

pro

cessin

g

Co

mp

lian

ce r

eco

rdin

g

Co

nti

nu

ou

sly

Cyclic

Sta

nd

ard

Sam

ple

Em

pir

ical C

alib

rati

on

Am

bie

nt

Lim

its

(°C

)

Ran

ge in

Btu

Fu

ll S

cale

Accu

racy ±

% o

f Fu

ll S

cale

Sp

eed

of

Resp

on

se (

90%

)

GROSS CALORIFIC VALUE

Water ∆T √ – √ – √ – – – √ – √ – √ 22÷25 130÷3,300 0.5 3 min

Air ∆T √ – √ – √ – – – √ √ – √ – 22÷25 120–3,600 0.5 15 min

Gas Chromatograph – √ √ √ √ √ – √ √ √ – √ – –18÷38 Any 0.5 10 min

Adiabatic Flame Temperature √ – √ √ √ – – – √ √ – √ – N/A N/A 0.5 N/A

NET CALORIFIC VALUE

Airflow Calorimeter √ – √ √ – √ √ √ – √ √ √ – 10÷32 130÷3,300 1.0 8 sec

Gas Chromatograph – √ √ √ – – – – – – √ √ – –18÷53 Any 0.5 10 min

Expansion Tube Calorimeter √ – √ – – – √ √ – √ – √ – N/A 120÷3,300 1.0 3.5 min

Specific Gravity – √ √ √ – √ √ – – √ – – – –18÷53 Varies 2.0 N/A

Process Chromatograph √ – √ – – – √ – – √ – √ – 16÷32 150÷3,600 2.0 4.5 min

Thermopile Calorimeter √ √ √ – – √ – √ – √ – √ – N/A 150÷3,300 2.0 55 sec

WOBBE INDEX

Airflow Calorimeter √ – √ √ – √ √ √ – √ – √ – 10÷43 130÷3,300 0.75 8 sec

Gas Chromatograph – √ √ √ √ √ – √ √ – √ √ – –18÷49 Any 0.5 10 min

Expansion Tube Calorimeter √ – √ – – – √ √ – √ – √ – N/A 120÷3,300 1.0 3.5 min

Thermopile Calorimeter √ – √ – – √ √ √ – √ – √ – N/A 150÷3,300 2.0 55 sec



Table 7: Carbon Dioxide Types of Sensors Nondispersive infrared (NDIR) Gas filter correlation (GFC) Orsat

Sample Pressure Up to 104 kPa, but atmospheric or near atmospheric is normal

Sample Temperature Up to approximately 49ºC, not a consideration when freeze-out trap is used

Sample Flow Rate Generally less than 2.35x10–4

m3/sec); typically 1÷2 l/min

Accuracy Can be as high as ±0.2 ppm; typically ±1%÷±2% of full-scale range 1%÷2% of full scale, including drift Laboratory procedure

Ranges 0÷2000 ppm 0÷3000 ppm 0÷5000 ppm 0÷1% 0÷2% 0÷5% 0÷10% 0÷20% 0÷100%

0÷5 ppm 0÷10 ppm 0÷20 ppm 0÷50 ppm 0÷100 ppm 0÷500 ppm 0÷1000 ppm 0÷2000 ppm (low detectable limit is 0.1 ppm)

–

Response Determined by cell volume and sampling rate; typically less than 30 sec 90 sec with 30 sec signal averaging time

–

Costs ($) 1500 (portable, battery-operated, diffusion type monitor with two alarm settings, digital display, and 4- to 20-mA output) 10,000 (permanently installed, explosion-proof NDIR analyzer with recorder).

Typical applications

Gas Minimum Range (ppm)

Maximum Range (%)

Ammonia (NH3) 0÷300 0÷10

Butane (C4H10) 0÷300 0÷100

Carbon dioxide (CO2) 0÷10 0÷100

Carbon monoxide (CO) 0÷50 0÷100

Ethane (C2H6) 0÷20,000 0÷10

Ethylene (C2H4) 0÷500 0÷100

Hexane (C6H14) 0÷200 0÷5

Methane (CH4) 0÷2,000 0÷100

Nitrogen oxide (NO) 0÷500 0÷10

Propane (C3H8) 0÷300 0÷100

Sulfur dioxide (SO2) 0÷500 0÷30

Water vapor (H2O) 0÷3,000 0÷5

– –

IR applications summary

Organic Vapors Analyzer

Carbon Monoxide

Carbon Dioxide

Simple Molecules

Complex Molecules

Organic Liquids

Solids (Reflection)

Comments

NDIR √ √ √ – – – Single-component analysis: ethylene, CO, acetylene, methane, etc.

Mid-IR filter √ √ √ √ √ – Single-component analysis: same as above, including ammonia, vinyl chloride, carbon tetrachloride, methyl ethyl ketone, ethylene dichloride, etc.

Near-IR filter – – – – √ √ Single-component analysis: ethylene dichloride, water, phenol, methyl alcohol, etc.; moisture in solids

Correlation spectrometer √ – – – – – Stack analysis, single-component gas analysis

Multiple-filter near-IR – – – – – – Multiple components for cereal, meat, and paper analysis

Multiple-filter mid-IR √ √ √ √ √ – Automotive exhaust analysis (CO, CO2,–CH); multiple components for mike analysis, multiple components of gases using a programmable circular variable filter



Table 8: Carbon Monoxide Detector Types Nondispersive infrared (NDIR); Mercury

vapor Gas chromatography

Electrochemical fuel cell

Catalytic oxidation Others (from color change badges, dosimeter tubes, and radon canisters to mass spectrometers)

Reference Method Infrared

Application For ambient air monitoring, electrochemical sensors are used most often; for detecting stack gas concentration, infrared sensors are used most often

Ranges For ambient For other applications, including stack gas 0÷1 ppm 0÷200 ppm 0÷5 ppm 0÷500 ppm 0÷10 ppm 0÷1000 ppm 0÷20 ppm 0÷2000 ppm 0÷50 ppm 0÷5000 ppm 0÷100 ppm 0÷10,000 ppm

0÷50 ppm 0÷200 ppm 0÷50 to 0÷500 ppm or more

0÷500 ppm

–

Sensitivity 1 ppm (generally) 0.1 ppm (chromatographs) 0.05 ppm (mercury vapor analyzers)

Response Times Infrared units are usually adjustable down to a few seconds, while electrochemical sensors require 30÷60 sec.

Accuracy ±1% of full scale for up to 1000 ppm and ±2÷3% of full scale for higher ranges (NDIR sensors) 2÷4% of reading (infrared stack gas analyzers) 1÷3% of full scale (electrochemical ambient monitors )

Costs ($) 400÷700 (pocket-size, battery-operated personal toxic gas monitor) 400÷2000 (continuous industrial electrochemical or infrared monitor/alarm/transmitter) 2000÷5000 (portable,battery-operated flue gas analyzer) 7500 (mercury vapor analyzer) ~10,000 (NDIR with recorder included) 25,000 and up (gas chromatograph)

Typical applications


Maximum Range (%)

Ammonia (NH3) 0÷300 0÷10

Butane (C4H10) 0÷300 0÷100



Ethane (C2H6) 0÷20,000 0÷10

Ethylene (C2H4) 0÷500 0÷100

Hexane (C6H14) 0÷200 0÷5

Methane (CH4) 0÷2,000 0÷100


Propane (C3H8) 0÷300 0÷100



– – – – –

Atmospheric Carbon Monoxide Analyzers

Detection Method Range, ppm Sensitivity, ppm Advantages Disadvantages

NDIR 0÷25 0÷50 0÷100

0.5÷1 U.S. reference method, accurate, stable, dry gases Sensitive, water, and CO2 interferences (correctable), zero gas problems

Mercury vapor (hot HgO + CO releasing Hg vapor) 0÷50 0.05 Sturdy, accurate, dry gases, high sensitivity Interferences by water and other gases

Gas chromatography (reduction of CO to CH4, flame ionization detection)

0÷200 0.1 Accurate, high sensitivity, also read CH 4, dry gases Complex and expensive



Table 9: Chlorine Methods of Detection Colorimetric Amperometric/ Polarographic Iodometric

Visual Spectrophotometric Amperometric Polarographic

Sampling All three methods can be used both on grab samples and as automatic continuous analyzers

Sample Pressure Generally atmospheric or near atmospheric. For continuous analyzer, water pressure is reduced to atmospheric.

Sample Temperature All methods are generally limited to the range of 0÷49ºC, with amperometric/polarographic method employing automatic temperature compensation within this range. Colorimetric method may or may not require precise temperature control, depending on the reagents employed.

Sample Size of Flow Rate

Grab samples as small as 5 ml are sufficient.

Flow rates of 10÷75 ml/min are generally specified.

Flow rates of 100÷750 ml/min are required

Design probes are available for in situ installations without sampling

–

Materials of Construction

Enclosures for units are available in fibreglass, styrene, urethane-painted steel, vinylcovered aluminum, and other corrosion-resistant construction, suitable for modular or control panel installation. Wetted parts are constructed of polyvinyl chloride (PVC), Teflon, Lucite, polyethylene, or glass. In amperometric/ polarographic method, gold or platinum measuring and copper reference electrodes generally are employed.

Specificity Determine either free or total residual chlorine Measures total residual chlorine.

Interferences Interfering substances may include other oxidants, e.g., manganese, nitrite, and chlorine dioxide, as well as turbidity and color

Nitrogen trichloride and chlorine dioxide may interfere with free chlorine determinations. –

Accuracy Generally ±2÷5% of full scale for ranges up to 20 ppm

Ranges 0÷1 ppm free chlorine 0÷3 ppm total chlorine 0÷5 ppm total chlorine 0÷10 ppm total chlorine

0÷0.1 ppm 0÷1 ppm 0÷2 ppm 0÷5 ppm 0÷10 ppm 0÷20 ppm or higher are available. The three-electrode units can measure chlorine residuals from the parts per billion (ppb) range to as high as 60 mg/l.

0.001÷10 mg/l.

Response to Chlorine Concentration Change

– Three minutes or more Generally less than 10 sec (continuous analyzer)

–

Cost ($) 25÷100 (visual test kits) ~1,800 (a portable amperometric titrator) ~2,000 (a free chlorine electrode in acrylic flow cell and with residual chlorine controller) ~8,000 (a corrosion-resistant amperometric transmitter system with probe cleaner) + 3,000 or more (the yearly cost of chemicals and maintenance) ~8,000 (polarographic transmitters ), but the cost of chemicals is much less

Relative Merits of Colorimetric and Amperometric Analyzers

Consideration Colorimetric Amperometric

Type of sample Better suited for clarified natural or treated waters than for highly turbid or colored waters and wastewaters

Turbidity and color generally not a problem; applicable to both treated water and wastewater

Interference Interfering ions should be absent; oxidized manganese compounds produce serious interference

Copper and silver ions may interfere by plating out on electrodes

Sample temperature Temperature control may or may not be required, depending on reagent employed

Manual or automatic temperature compensation required

Speed of response Generally 3 min or more required to detect a change in chlorine concentration

Chlorine concentration change detected in 10 sec or less

Calibration Analyzer precalibrated; periodic standardization requires only simple manipulations

Periodic calibration required by separate analytical technique

Reagents required External reagent solution required External buffer may be required for varying sample pH

Maintenance stability Cell staining may require periodic cleaning Electrodes may require periodic cleaning

Stability Drift compensated for by relatively simple standardization step

Drift not a problem when electrodes are kept clean

Initial cost Generally less expensive Generally more expensive

–



Table 10: Gas Chromatographs Type of Sample Vapor or vaporizable liquid

Sample Pressure 1÷7 bar

Ambient Temperature –20÷50°C; however, a sheltered environment is recommended

Analysis Zone 60÷180°C provided that the desired oven temperature is at least 10°C above ambient (stable oven temperature ±0.05°C at steady ambient ±0.5°C for –20÷50°C ambient change

Contacting Material Stainless steel or surface-deactivated steel for trace analysis of reactive compounds, Teflon

Auxiliary Utilities Instrument air-dry, oil-free, available at min 3.5 bar and 1÷1.5 sl/sec; carrier gas, zero air, and hydrogen for FID; possible steam tracing or electrical heating for sample lines

Cycle Time 2÷20 min, depending on application and packed or capillary column operation

Special Features Accepts other inputs (e.g., flow rate and density in the calculation of output, e.g.,BTU/h); built-in diagnostics with local and remote indication; multicomponent readout; stand-alone or networked; communication link (fieldbus or Ethernet directly to the plant or local LAN and local control system); local and remote operator interface; single- or multistream analysis

Location Class 1, Groups B, C, and D, Division 1 hazardous areas

Analyzer Cost ($) 35,000÷45,000 (basic analyzer, depending on number purchased)

Installed Cost ($) 45,000÷125,000 (depending on type, number, and application)

Components of process gas chromatographic system Process Gas Chromatograph (PGC) Analyzer Programmable controller

Sample Handling and Sample

Conditioning System (SHS/SCS) Oven

Column 1. Packed Columns 1.1. Conventional 1.2. Micropacked 2. Capillary

Sample 1. Sample Injection 2. Backflush 3. Heart-cutting

Column switching valves 1. Rotary valve 2. Sliding plate valve 3. Diaphragm valve

Detectors 1. Thermal Conductivity Detector 2. Flame Ionization Detector 3. Flame Photometric Detector 4. Pulsed Flame Photometric Detector 5. Orifice-Capillary Detector 6. Miscellaneous Detectors 6.1. Photoionization Detector 6.2. Electron Capture Detector 6.3. Discharge Ionization Detectors

Carrier gas 1. Flow control 2. Pressure control

a. Programmer b. Peak Processor c. Data Acquisition d. Input–Output e. Communication f. Operator Interface g. Alarms and Diagnostics h. Quantitation

a. Sample Probe b. Sample Transport c. Sample Conditioning d. Multistream Analysis e. Sample Disposal



Table 11: Liquid Chromatographs Types Laboratory: thin-layer and paper chromatography

Column Liquid–solid absorption, liquid–liquid partition, gel permeation (exclusion), and ion exchange

Detectors Fiber-optic probes, differential refractive index, fixed- or variable-wavelength ultraviolet, dielectric constant, electrical conductivity

Type of Sample Liquid

Sample Pressure 35÷7,000 kPa

Sample Temperature 16÷149ºC

Ambient Temperature −18÷50ºC

Contacting Materials Stainless steel, Teflon standard; all conventional materials available

Utilities Required Electrical power, carrier solvent, air at 700 kPa

Repeatability ±0.5% for most applications

Cycle Time 3÷20 min for most applications

Costs ($) Laboratory system component costs: 300÷1,800 (HPLC columns) 2,000÷5,000 (solvent delivery pumps) 2,500 (fixed-wavelength ultraviolet–visible (UVVIS)detectors) ~5,000 (variable-wavelength detectors) ~3,000 (microprocessor based data acquisition integrator) ~50,000 (complete process HPLC units) + ~100,000 (their installed cost)

Components of process liquid chromatographic system

Process Liquid Chromatograph (PGC) Analyzer Programmable controller

Sample Handling and Sample Conditioning System (SHS/SCS)

Oven

Column 1. Liquid–Partition Columns 2. Liquid–Adsorption Columns 3. Gel–Permeation Columns 4. Ion Exchange Columns 5. Electrophoresis

Sample

Column switching valves

Detectors 1. Optical Absorbance Detector 2. Refractive Index Detector 3. Dielectric Constant Detector

Carrier supply

a. Programmer b. Peak Processor c. Data Acquisition d. Input–Output e. Communication f. Operator Interface g. Alarms and Diagnostics h. Quantitation

a. Sample Probe b. Sample Transport c. Sample Conditioning d. Multistream Analysis e. Sample Disposal



Table 12: Colorimeters Types Spectrophotometers Colorimeters

Methods One-dimensional Tristimulus One-dimensional Tristimulus

Types of Samples Liquid, gas, or solid

Wavelength Ranges 200÷1,000 nm (typical)

Spectral Resolution 2÷20 nm

Source Lamp Halogen, Xenon flash, LED, IR, fluorescent, fiber optics

Detectors CCD and photodiode linear arrays or photocells

Materials of Construction Standard materials, ordinary or quartz glass

Cell Length 0.5÷1000 mm

Sample Pressure Vacuum÷10.6 bars

Accuracy 1 nm (array spectrophotometers) 1%

Costs ($) 100 (a single-channel color analog channel) 1,000 (fiber-optic spectrophotometers) 20,000÷60,000 (on-line scanning systems)

Color and Wavelength Association

Approximate Wavelength (μm) Associated Color

400–450 Violet

450–500 Blue

500–570 Green

570–590 Yellow

590–610 Orange

610–700 Red

Table 13: Combustibles Types Measurement of filament temperature or resistance in catalytic

combustion sensors is most common. Thermal conductivity is used at higher concentrations. Electrochemical and semiconductor sensors can be used when hydrogen and other known gases are to be detected.

Flame ionization and photoionization with or without a chromatograph can be used for accurate hydrocarbon detection. Response varies and gases of concern need to be known in the design and selection phase of the project.

Infrared can be used for both point and area (open-path) applications. It cannot detect hydrogen.


Many choices exist and offer the opportunity to select an appropriate one for a given application. Stainless steel and polymer sensor heads with ceramic and metal sensors are usually offered. Various polymer and metal constructions with the appropriate optical window selections for photoionization and infrared applications are available.

Accuracy 5% of lower explosive limit (LEL); linearity and repeatability 2÷3% of LEL ppm concentrations can be detected and monitored ppm and low % LEL levels achievable, but vary dramatically and usually more a function of the application than the instrument

Drift 1÷3% of LEL per month No generally accepted drift range per value No generally accepted drift range per value

Costs ($) 300÷1,000 (a battery-operated portable gas leak detector with sensing probe) 2,500 (a combined oxygen and combustibles sensor, microprocessor based, portable with diffusion sampling) 1,000÷2500 (the cost per channel for a permanently installed single-channel monitor with alarm or for a multichannel system) 3,000÷5,000 (the cost per channel increases for sampled remote head installations, due to the installation cost of tubing) 5,000÷10,000 (the cost per channel increases when a flame ionization or photoionization detector is used) 15,000÷20,000 (a portable chromatograph with electrochemical detector and 50-ppb sensitivity) 1,200÷2,700 (a point-infrared system) 7,000÷20,000 (an open-path infrared system)

Properties of Some Flammable Liquids and Gases

Flammability Limits in Air (% vol.) Material Specific Gravity Air = 1 Ignition Temperature in Air (ºC)

Lower Upper

Methane (CH4) 0.55 645 5.3 15.0

Natural gas (Blend) 0.65 628 4.5 14.5

Ethane (C2H6) 1.04 534÷596 3.0 12.5

Propane (C3H8) 1.56 514÷588 2.2 9.5

Butane (C4H10) 2.01 489÷569 1.9 8.5

Toluene (C7H8) 3.14 552÷555 1.3 6.7

Gasoline (A blend) 3÷4.00 333 1.4 7.6

Acetone (C3HO) 2.00 561 2.6 12.8

Benzene (C6H6) 2.77 520 1.4 6.7

Carbon monoxide (CO) 0.97 644÷658 12.5 74.0

Hydrogen (H2) 0.07 580÷590 4.0 75.0

Hydrogen sulfide (H2S) 1.18 346÷379 4.3 45.0

Note: LEL = Lower explosive limit (The lowest concentration of gas or vapor in air where, once ignition occurs, the gas or vapor will continue to burn after the source of ignition has been removed) UEL = Upper explosive limit (The highest concentration of gas or vapor in air in which a flame will continue to burn after the source of ignition has been removed) Flash point = The lowest temperature at which a flammable liquid gives off enough vapors to form a flammable or ignitable mixture with air near the surface of the liquid or within the container used. Many hazardous liquids have flash points at or below room temperatures. They are normally covered by a layer of flammable vapors that will ignite in the presence of a source of ignition.



Table 14: Conductivity Analyzers Type Two-electrode cell Four-electrode cell Electrodeless cell

Principle Ionic concentration of electrolyte samples

Standard Design Pressure Up to 3.5 MPa

Standard Design Temperature Up to 200°C

Element Materials Cells: glass, epoxy, and stainless steel. Electrodes: platinum, nickel, titanium, and carbon

Epoxy, Noryl, PFA, PEEK (polyether ether ketone), and polypropylene

Range 0÷0.05µS/cm minimum; 0÷2S/cm maximum

Accuracy (of full scale) Up to ±0.5%

Cost ($) 700 (an analyzer with these features: panel-mounted monitor, general-purpose electrical class; NEMA 1 environmental protection; ±1% accuracy; RFI/EMI protection; two-electrode contacting sensor with 3/4-in. NPT process connection; single analog output) 1500 (an analyzer with these features: pipe or surface-mounted field monitor; Division 2 electrical class; NEMA 4X environmental protection; ±0.5% accuracy; RFI/EMI protection; high-temperature electrodeless sensor capable of measuring hot acid, base, or salt solutions; dual analog outputs)

Typical applications Clean solutions to avoid errors

caused by the formation of

coatings and films on the

electrodes

High conductance when coating

and fouling of electrodes are a

concern

Eliminate the electrode polarization effects

Conductivity applications

Process Application (Usage) and Comments

Chemical streams To measure and control solution strength.

Steam boilers Blowdown is a method of lowering the amount of dissolved solids in a boiler by dilution. To control buildup of dissolved solids to prevent scaling and corrosion. Condensate return is usually checked for quality before being returned to the boiler. If out-of-limits, it is dumped.

Waste streams A means of determining the amount of dissolved salts being discharged

Cooling towers Bleed control is a method of reducing the total dissolved solids in a tower by dilution (similar to blowdown). To prevent scaling and corrosion. For bleed control, the electrodeless conductivity system works best to minimize maintenance and failure.

Fruit peeling Strong caustic is used, and its strength can be determined by conductivity.

Rinse water Plating shop running rinse water is monitored for dissolved salts—a method of reducing water consumption.

Semiconductor rinse water

Requires ultrapure water, usually measured in mega-ohms/centimetre.

Interface determination Usually used in food processing, e.g., dairy and brewing. Most commonly used in cleaning in place (CIP); interfaces in pipes are easily determined and can be diverted by valves controlled by conductivity.

Demineralizer output Determination of ion exchange exhaustion.

Reverse osmosis Efficiency of reverse osmosis (RO) operations is usually monitored by comparing inlet and outlet conductivity or TDS ratio (cell 1/cell 2). The inlet conductivity is installed upstream of the RO feed pump to avoid high pressure requirements. Also, abnormal readings can be used to diagnose membrane fouling, improper flow rate, membrane failure, etc.

Desalination Similar to reverse osmosis and demineralization process.

Deionization process Conductivity or resistivity measurement provides capability for monitoring and controlling the acid and caustic dilution. Regeneration of deionizers requires consistent application of acid and caustic to obtain repeatable results. Savings is provided by consistent regeneration, which assures deionized water availability, less frequent regeneration, long resin life, and conservation of costly reagents. More precise control can be obtained by using conductivity ratio measurement. A comparison of inlet and outlet (ratio of cell 1/cell 2) conductivity across the bed can determine the unwanted ions and the need for bed regeneration, which can compensate and control for variations in mineral concentration of feed water.

Ion exchange Occasionally loses resin. If a resin bead or fines are trapped between the electrodes of a cell, it is shorted and produces a very low resistivity (or high conductivity) reading. This feature is a great help in troubleshooting.

Note: TDS = Total dissolved solids



Table 15: Consistency Analyzers Types Blade Rotary Probe Optical Microwave Radiological

Element Materials Stainless steel and titanium

Normal Design Temperature Up to 120ºC

Normal Design Pressure Up to 8.6 bars

Range 0.01÷15% consistency

Sensitivity 0.01÷0.03% consistency

Repeatability 0.5% of reading

Accuracy Function of empirical calibration, usually 1% of reading

Cost (%) 3,000÷10,000 (laboratory units) 6,000÷30,000 (continuous industrial units)

Applications Wood pulp, dough, tomato paste, paint, gelatin, or drilling mud

Note: Consistency = a percentage by dividing the mass of solid material by the total mass of a wet sample, resulting in units of mass per unit mass

Table 16: Corrosion Monitoring Type Electric resistance Linear polarization resistance

Design Pressure Up to 422 bars –

Design Temperature Up to 560ºC –

Materials of Construction Wide range of corrosion-resistant metals or alloys

Cost ($) 3,000÷5,000

Instrumentation for Corrosion Monitoring

Method Measures or Detects Advantages Limitations

Corrosion coupon

Average corrosion rate over a known exposure period by weight loss

1. The technique is suitable for all environments.

2. Coupons provide information about the type of corrosion present. Coupons can be

examined for evidence of pitting and other localized forms of attack.

3. There are a variety of coupons available for specialized analysis.

1. High corrosion rates for short periods of time may be undetectable and cannot

be correlated to process upset conditions.

2. The technique requires plant shutdowns for installation or removal. Highly

qualified personnel and reasonably sophisticated test procedures are required for

the interpretation of the results. Linear polarization

Corrosion is measured by electrochemical polarization resistance method

1. The polarization probes measure corrosion rate almost instantaneously. They

measure the instantaneous corrosion rate instead of the average corrosion rate.

2. The probes are useful for comparing relative corrosion rates. Thus, it is possible to

use the data to determine the process variables that give the lowest corrosion rates.

3. The commercially available polarization probes supply pitting tendency

information.

1. The probes will not work in nonconductive fluids or fluids containing

compounds that coat the electrodes (e.g., crude oil).

2. The absolute accuracy of the corrosion measurement is not as reliable as the

one obtained from corrosion coupons.

3. The method measures the combined rate of any electrochemical reactions at

the surface of the test sample. If reactions other than corrosion reactions are

possible at comparable or greater rates, the measured rate will also include these

other reactions. Electric resistance

Metal loss is measured by the resistance change of corroding metal element

1. The technique is suitable for all environments except liquid metals or some

conductive molten salts. The process material, which causes the corrosion, need not

be an electrolyte (in fact, it need not be a liquid).

2. A corrosion measurement can be made without having to see or remove the test

sample.

3. Corrosion measurements can be made quickly—in a few hours or days—or

continuously. Sudden increases or decreases in corrosion rate can be detected, so that

the user can modify the process to reduce the corrosion.

4. The method can detect low corrosion rates that would take a long time to detect

with weight-loss methods. Its accuracy is comparable to the coupon method

1. The technique is usually limited to the measurement of uniform corrosion only

and is not generally satisfactory for localized corrosion.

2. The probe design includes provisions for temperature variations. This feature is

not totally successful. The most reliable results are obtained in constant-

temperature systems.

3. The technique does not provide an instantaneous corrosion rate, so any

corrective actions must be delayed until an average corrosion rate can be

determined.

4. The resistance method measures a combination of chemical and physical

erosion without distinguishing between the two. Analytical pH of process stream – –

Radiography Flaws and cracks by penetration of radiation and detection on film

– –

Ultrasonics Thickness of metal and presence of cracks, pits, etc., by changes in response to ultrasonic waves

– –

Eddy current testing

Use of a magnetic probe to scan surface – –

Hydrogen sensing

Hydrogen probe used to measure hydrogen gas liberated by corrosion

– –

Analytical Concentration of corroded metal ions or concentration of inhibitor; oxygen concentration in process stream

– –

Potential monitoring

Potential change of monitoring metal with respect to a reference electrode

– –



Table 17: Differential Vapor Pressure Sensor Purpose Compare vapor pressure of reference fluid to that of process fluid

Wetted Parts 316 stainless steel

Typical Ranges From 254–0–254 mm H2O up to 10.8–0–10.8 m H2O)

Maximum Working Pressure 105 bars

Maximum Working Temperature: 121°C

Ambient Effect 1% or less per 55°C

Repeatability 0.1% of span

Dead Band 0.1% of span

Accuracy 0.5% of span (better with microprocessor-based transmitters)

Cost ($) 1,500 (the cost of a d/p transmitter) 2,500 (the cost of a d/p transmitter, a temperature bulb, and attaching and filling the bulb with the desired reference fluid)

Limitations of the analyzer 1. It correctly reflects the composition of only binary materials 2. It is essential for a successful installation that the reference fluid be stable 3. There can be a transient upset if the column pressure changes faster than the pressure in the reference bulb can follow.

Table 18: Dioxin Analysis Type of Sample Gas sample containing particulate

Standard Design Pressure Generally atmospheric or near atmospheric

Standard Design Temperature –32÷815ºC

Sample Velocity 2÷50 m/sec

Materials of Construction 316 or 304 stainless steel for pitot tubes; nickel, nickel-plated stainless, quartz, or borosilicate glass for nozzles

Cost ($) 8000÷16,000 (a complete EPA particulate sampling system (EPA Reference Method 23) 75,000÷100,000 (laboratory-scale GC-MS unit)

Applications Sampling and analysis of recalcitrant dioxin compounds. These measurements are required in ecological risk assessment and in the determination of the toxicity of various samples. The U.S.

Environmental Protection Agency (EPA) regulates emissions from municipal waste combustors (MWCs) and sets emission limits for polychlorinated dibenzop -dioxines (PCDDs) and polychlorinated

dibenzofurans (PCDFs). This is a summary of the proposed Method 23 for measuring the emissions of PCDDs and PCDFs from MWCs.

Note: EPA = The U.S. Environmental Protection Agency GC-MS = Gas Chromatography-Mass Spectrometry

Table 19: Elemental Monitors

ICP (inductively coupled plasma) analytical atomic spectrometer Type of Instrument

ICP-OES (optical emission spectrometer) ICP-AES (atomic emission spectrometer) ICP-MS (mass spectrometer)

XRF (x-ray fluorescence) spectrometer

Element Range Virtually all elements –

Cost ($) 50,000÷200,000 – 140,000÷350,000 200,000÷300,000 (on-line) 10,000÷30,000 (portable)

Typical applications Detection of sulfur (S) and lead (Pb) in refineries Measurement of oxides in such raw materials as limestone, sand, bauxite, ceramics, slags, and sinters Sensing of major and minor elements (Cu, Fe, Ni, etc.) in food and chemical products



Table 20: Fiber-Optic Probes Type of Process Fluid Liquids Solids Gases

Standard Design Pressure Up to 70 bar

Standard Design Temperature Up to 480ºC

Materials of Construction Stainless steel (others are available), sapphire, sealing materials

Costs ($) 1,000 (wand probe with tip) 2,500 (spectra-calliper probe) 2,000÷20,000 (fiber-optic spectrophotometer systems)

Typical applications Toxic, corrosive, radioactive, explosive, high- or low-temperature or -pressure, and noisy

environments

Fiber optic techniques Glass Optical Fiber Plastic Optical Fiber

Probes Wand Probe Spectra-Calliper Probe Transmission Probe Long-Path-Flow Tube Gemstonetips (GEM) Probe Six-to-One Probe

Approaches for qualitative and quantitative chemical analysis.

Absorption Fluorescence (Optrodes, Oxygen Probe) Scattering Refractive Index

Table 21: Fluoride Analyzers Principles of Operation

Detector tubes Electrochemical Paper tape

Ion mobility spectrometry

Infrared spectrometry

Ion-specific electrodes Silicon dioxide sensors Ion chromatography Titration Colorimetric Gas chromatography


Surfaces of equipment contacting fluoride should be stainless steel, Teflon, epoxy, polyethylene, or polypropylene

Concentrations Measured

Monitoring for worker protection is usually in the 0÷10 ppm range. Leak detection in the surroundings of hydrogen fluoride (HF) handling equipment requires sensitivity in the high parts per million (ppm) range. Monitoring for low-level environmental damage may require sensitivity in the parts per billion (ppb) range.

Sensitivity Range 0.1÷20 ppm Low ppm Low ppm

0.05÷10 ppm Low to mid ppm

Low ppb to high ppm, function of sampling time, volume

Qualitative response to high ppm levels

Measurement is usually in the ppm range; sensitivity depends on sampling parameters.

Calibration Calibration of vapor analyzers usually is performed with permeation-type devices or with calibrated gas standards. Liquid phase analyzers are calibrated using solutions of an appropriate fluoride compound such as sodium fluoride.

Accuracy ±20% of actual measurement at low humidities, inaccurate at high humidities

±10% of full scale Varies with type of instrument and humidity level

These laboratory and automated techniques are capable of providing high accuracy (±3% of actual measurement) under ideal conditions, but this is often compromised by inaccurate sample collection practices.

Qualitative only These laboratory and automated techniques are capable of providing high accuracy (±3% of actual measurement) under ideal conditions, but this is often compromised by inaccurate sample collection practices.

Cost ($) 3/analysis, 50/sampling kit

1,000÷3,000 3,500/point

17,000 – – – – – – –

Automatic or Manual Method

M A A A A/M* A M M A/M* A/M* A

Suitable for Water Analysis

No No No No Yes No Yes Yes Yes Yes No

Gas or Particulate Measurement

G G G G G/P** G G/P** G/P** G/P** G G

Suitable for Stack/Process Monitoring

No Some*** Some***

Yes Some*** Leak detection Some*** Some*** Some*** Some*** Some***

Suitable for Organic Fluoride Monitoring

Yes**** No No Yes**** No No No No No Yes Yes

Note: * = Manual method can be performed in lab; automatic systems are available ** = Particulate measurement requires special collection techniques *** = Suitability for stack monitoring depends on moisture present, interference, etc. **** = Required pyrolysis equipment available from manufacturer; other methods may be adapted with custom equipment



Table 22: Hydrocarbon Analyzers Total hydrocarbon

Methane Hydrocarbon classes Individual hydrocarbons

Type of Measurements

Flame ionization

Chromatography Flame ionization Mass spectrometry Flame ionization Mass spectrometry

Infrared Chromatography

Hydrocarbon dew point in natural gas (chilled mirror)

Ion mobility spectroscopy

Laser-induced absorption radar

Reference Method

Gas chromatography with flame ionization for nonmethanes

Sensitivity 0.1 ppm 50 ppb (followed by electrochemical sensor)

0.1 ppm – 0.1 ppm – – 50 ppb (followed by electrochemical sensor)

– – –

Ranges From 0÷10 ppm to 0÷100% lower explosive limit (LEL)

Accuracy ±1%

Costs ($) 10,000÷20,000 25,000÷100,000 15,000 (portable with electrochemical detector)

10,000÷20,000 50,000÷250,000 10,000÷20,000 50,000÷250,000 10,000÷20,000 25,000÷100,000 15,000 (portable with electrochemical detector)

Atmospheric Hydrocarbon Analyzers

Hydrocarbon Type

Method Limitations and Interferences

Total (as carbon) FID Some response to carboncontaining nonhydrocarbons

Methane GC Expensive equipment (can also be used for carbon monoxide)

Column preparation fussy column and FID Methane only subtractive

Mass spectrometry Freeze-out required, expensive

Subtractive columns and FID Column preparation fussy

Mass spectrometry Freeze-out required, expensive, data reduction requirements large

Infrared spectrometry Freeze-out required, expensive, not total class coverage

Ion mobility spectrometry Clean sample required, limited knowledge in industry

Laser-induced absorption Expensive, specialized support required

Aromatics, olefins, paraffins

Perimeter monitoring Concentration/unit length rather than point value

Individuals GC Expensive, data reduction requirements large

Table 23: Hydrogen Sulfide Analyzer Types Electrochemical gas diffusion Solid-state or gold-film sensors Tape staining UV photometric Gas chromatography

Ranges 0÷50 ppm is typical for ambient air monitors, with maximum range up to 0÷500 ppm. For process applications, ranges up to 0÷100% are available.

Accuracy 3÷5% of full scale for air monitors; 1% of full scale for process analyzers

Costs ($) 600÷1000 (pocket-size, battery-operated monitor) 2500 (portable microprocessor based diffusion-type unit) >20,000 (UV photometric and chromatographic analyzers)

Applications Personnel safety, environmental protection, and process control (ambient and on-line measurements)



Table 24a: Infrared Analyzers Electromagnetic spectrum Wavelengths of 2500÷20,000µm

Design Single-Beam Configuration Dual-Beam Configuration

Types Laboratory scope (Grating Spectrophotometers, Filter Spectrometers, Fourier Transform Spectrometers and Tunable Lasers) Process scope (Fourier transform spectrophotometer (used both on lab and online), Single-Component Analyzers, Gas Filter Correlation Spectrometers, Filter Analyzers, Multiple-Component Fixed Filter Analyzer and Programmed Circular Variable Filter Analyzer)

Process Streams Gas or liquid, with surface analysis of solids

Application and Minimum Full-Scale Range Maximum range is usually 100%, with path length adjustment; minimum range, assuming 10-m path length. Ammonia—100 ppm Carbon monoxide—25 ppm Carbon dioxide—20 ppm Ethylene—100 ppm Hexane—100 ppm Methane—10 ppm Moisture (humidity)—50 ppm Nitrous oxide—10 ppm Propane—100 ppm Sulfur dioxide—100 ppm Notes: 1. Some of these analytes can be done very well in the UV, for example, sulfur dioxide. 2. The minimum range is also a function of the matrix—the minimum for benzene in air is going to be much lower than that for benzene in gasoline. 3. The normal range is a factor of 10, so ammonia could be 10÷100 ppm or 1÷10%, but not 100 ppm÷10%.

Operating Pressure Standard from atmospheric to 10 bars; special up to 70 bars

Ambient Operating Temperature –40÷50ºC is standard; probe temperatures can be higher with special arrangements

Humidity Limitations Up to 95% relative humidity (normally the instrument is purged, which negates the effect of humidity in the atmosphere.)

Materials of Construction Cell bodies are available in all standard materials; windows can be made of sodium chloride, calcium fluoride, barium fluoride, sapphire, or zinc selenide

Cell Lengths For liquids, from 0.1÷100 mm; For gases, up to 40 m enclosed and any length for open-path monitoring

Warm-Up Time 15÷20 min. (For most stable operation, allow 16 h for warm-up.)

Repeatability (of full scale) ±1%

Linearity (of full scale) ±0.5%

Accuracy (of span) ±2%

Drift ±1% of full scale for zero and the same for span per day

Costs ($) Note: The installation and upkeep costs are normally much larger than the vendor costs given below. 4000÷5000 (single-beam portable or laboratory units) 8,000 (an industrial non-dispersive infrared analyzer with diaphragm capacitor) 25,000÷27,000 (a multigas analyzer pulling in up to five gases from 50 m distances) 20,000 (a microprocessor-based portable spectrometer with preprogrammed multicomponent identification capability for ambient air monitoring and with space for 10 user-defined standards for calibration, AC/DC converter, sample probe, and carrying case) 75,000÷125,000 (an industrial FTIR)

IR Analyzer Applications Summary

Organic Vapors Analyzer

Carbon Monoxide

Carbon Dioxide

Simple Molecules

Complex Molecules

Organic Liquids

Solids (Reflection)

Comments

NDIR √ √ √ – – – Single-component analysis: ethylene, CO, acetylene, methane, etc.

Mid-IR filter √ √ √ √ √ – Single-component analysis: same as above, including ammonia, vinyl chloride, carbon tetrachloride, methyl ethyl ketone, ethylene dichloride, etc.

Near-IR filter – – – – √ √ Single-component analysis: ethylene dichloride, water, phenol, methyl alcohol, etc.; moisture in solids

Correlation spectrometer

√ – – – – – Stack analysis, single-component gas analysis

Multiple-filter near-IR

– – – – – – Multiple components for cereal, meat, and paper analysis

Multiple-filter mid-IR

√ √ √ √ √ – Automotive exhaust analysis (CO, CO2,–CH); multiple components for mike analysis, multiple components of gases using a programmable circular variable filter

Typical Applications for NDIR Analyzers


Maximum Range (%)

Ammonia (NH3) 0÷300 0÷10

Butane (C4H10) 0÷300 0÷100



Ethane (C2H6) 0÷20,000 0÷10

Ethylene (C2H4) 0÷500 0÷100

Hexane (C6H14) 0÷200 0÷5

Methane (CH4) 0÷2,000 0÷100


Propane (C3H8) 0÷300 0÷100





Table 24b: Near-Infrared Analyzers Electromagnetic spectrum Wavelengths of 0.8÷2500µm

Types 1. The filter instrument uses two or more filters to pick out reference and measuring wavelengths. These are the lowest-cost instruments and generally only measure one to a few analytes in the stream. 2. The dispersive units with single detectors and moving grating. The moving grating causes some wavelength instability that becomes a major problem with very sensitive measurements. 3. FTNIR is very similar to FTIR; however, since the frequency and wavelengths are inverse scales, at the shorter wavelengths in NIR there is a higher reproducibility factor required for the mirror movement. However, these have been successfully applied in some very rigorous applications, such as measuring the octane of gasoline. 4. The diode array instrument with no moving parts—note that the material of construction in the diode array sets the usable range of the instrument. The most common diodes are made from silicon that become transparent at wavelengths longer than 1100 nm; therefore, these diode arrays are only usable in the third overtone. [The diode array instrument has no moving parts but requires extreme temperature stabilization to prevent wavelength changes due to different distances between the grating and detector array as a function of temperature. One unit on the market controls the spectrograph temperature to ±0.1ºC, while the outside temperature varies from –40 to 50ºC.]

Process Fields Gas, liquid, or solid, but mostly liquid and solid

Some Applications Octanes of gasoline, 80÷100 Octanes of components of gasoline, 60÷120 Benzene in gasoline, 0.2÷1% Boiling points of gasoline, 50÷200ºC Cetane of diesel fuel Protein content of wheat Molecular weight of small polymers Caustic in water 0.1÷10% BTU of natural gas (high pressure) Active ingredient in drugs p-Xylene concentration in mixture of aromatics

Operating Pressure 10bar (standard) 70 bar (special)

Ambient Temperature –40÷50°C (standard) Note: Since the ambient temperature changes will affect the spectrometer, it will require temperature stabilization.)

Stream Temperature This restricts cell material only; normally one keeps the temperature constant.

Humidity Limitations None—NIRs, like IRs, should be purged; this eliminates the humidity problem.

Materials of Construction Cell bodies in all standard materials; windows can be quartz (most common), sapphire, and others

Cell Path Lengths For liquids, 1÷100 mm For gas, long (unless high pressure too long to be practical)

Warm-Up Time Manufacturers normally quote minutes—recommend overnight for best stability

Repeatability (of full scale) ±0.01%

Linearity (of full scale) ±0.5%

Accuracy (of span) ±1% (depends on how well the “modeling” has been done; can be much better)

Drift ±0.01% of full scale and the same for span per day

Costs ($) 80,000÷180,000 (depending on number of streams, distance between the analyzer and sample, and sample preparation required) Note: At one installation, the analyzer is determining 25 properties every 45 sec. At another installation, the plant estimated that the analyzer saved $15 million the first year it was in service. At some locations, the instrument is looking at multiple streams; with a 45-sec analysis time, it is possible to look at several streams and still update the control system as often as needed.)



Table 25: Ion-Selective Electrodes Types of Electrode Glass Solid state Solid matrix Liquid–ion exchanger (Liquid membrane) Gas sensing

Standard Design Pressure Generally dictated by electrode holder; 0 bar (solid state and liquid–ion exchanger) 0÷7 bar (the most electrode types) over 7 bar (for solid-state designs)

Standard Design Temperature

0÷50ºC (solid matrix and liquid–ion exchange) –5÷80ºC (the most others, with 100ºC intermittent exposure being permissible

Range From fractional parts per million (ppm) to concentrated solutions

Relative Error For direct measurements, an absolute error of ±1.0 mV is equivalent to a relative error of ±4% for monovalent ions and ±8% for divalent ions; for end-point detection or batch control, ±0.25% or better is possible; for expanded-scale commercial amplifiers, error is better than ±1% of full scale.

Costs ($) 120÷300 (electrodes) 600÷8,000 (systems) 50÷500 (hand-helds)

Ion/Species Sodium Bromide Cadmium Chloride Copper (II) Cyanide Iodide Lead Redox (platinum) Silver/sulfide Thiocyanate

Calcium Divalent cationa Nitrate

Calcium Chloride Divalent cationa Fluoroborate (BF4–), (boron) Nitrate Perchlorate Potassium

Ammonia Carbon dioxide Nitrite Sulfur dioxide

Lower Detectable Limit, ppm 0.02 0.04 0.01 0.2 0.006 0.01 0.006 0.2 Varies 0.01 Ag/0.003 S 0.3

0.2 0.001 0.3

0.2 0.2 0.001 0.11 0.3 0.7 0.04

0.009 0.4 0.002 0.06

Principal Interferences Ag+, H

+, Li

+, Cs

+, K

+, Tl

+ CN

–, I

–, S

–

Ag+, Hg

++, Cu

++, Fe

++, Pb

++

Br–, CN

–, S

–, SCN

–, I

–

Ag+, Hg

++, Fe

+++

S=, I

–

S=, CN

–

Ag+, Hg

++, Cd

++, Fe

++

All redox systems Hg

++

OH–, Cl

–−, Br

–, I

–, NH3, S2O3

=, CN

–, S

=

Zn++

, Fe++

, Pb++

, Cu++

, Ni++

, Sr++

, Mg++

, Ba++

– Cl

–, ClO4

–, I

–, Br

–

Zn++

, Fe++

, Pb++

, Cu++

, Ni++

, Sr++

, Mg++

, Ba++

ClO4

–, Br

–, I

–, NO3

–, OH

−, F

–, OAc

–, SO4

–, HCO3

–

– I–, HCO3

–, NO3

–, F

–

Cl–, ClO4

–, I

–, Br

–

Cl–, ClO3

–, I

–, Br

–, HCO3

–, NO3

–, etc.

Cs+, NH4

+, H

+, Ag

+, Tris

+, Li

+, Na

+

Volatile amines Volatile weak acids CO2, volatile weak acids CO2, NO2, volatile organic acids

Note: aWater hardness electrode is also known as the divalent cation electrode.



Table 26: Mass Spectrometers Type of Sample Vapor

Standard Design Pressure Atmospheric

Sample Temperature 50÷200ºC; sufficient to provide vapor sample with no condensation

Ambient Temperature 20÷25ºC

Contacting Materials Inlet materials of construction designed to be compatible with sample

Auxiliary Utilities Required: Sometimes cooling water

Cost ($) 3,000÷200,000 (depending on analyzer section, application complexity, and data report and collection accessories) 149,000 (time-of-flight section) 175,000 (with specialized data acquisition systems) 120,000 (magnetic section (food processing industry)) 3,500 (RGA) 3,000 (multiple purchase) 45,000÷90,000 (quadrupole section) 90,000÷150,000 (ion-trapping section)

Accuracy ±0.5% for most applications

Repeatability ±0.2% for most applications

Cycle Time 0.5÷4 sec per stream, depending upon applications

Special Features Multicomponent readout, database of mass spectra, programmable temperature control, coupled to gas or liquid chromatography units

Table 27: Mercury in Ambient Air Methods of Detection Ultraviolet, flameless atomic

absorption Atomic absorption spectrophotometer Gold-film sensor Colorimetric titration Gas chromatography Atomic fluorescence Neutron activation

Regulatory Levels for Emissions 100, 50, 10, and perhaps 5 µg/m3

Range, in Ambient Air 1÷200 ng/m3

Ranges of Analyzers 0÷400 volumetric ppb 0÷45 or 0÷75µg/m3 0÷2 mg/m3 – – – –

Sensitivity 1.0 ng/m3 is about the best attainable

0.1µg/m3 0.003 mg/m3 – – 0.1 ppm in liquid

impinger sample –

Accuracy 2% on direct measurement, 10% with concentrators

– 5% at 0.1 mg/m3 – – – –

Costs ($) ~25,000 (laboratory analyzer alone) ~30,000 (process analyzer alone) ~45,000 or more (an integrated sampler–detector system)

100,000 and up 5,000 (battery-operated, portable gold-film sensor with small flow pump)

– – – –

Table 28: Mercury in Water Method of Detection Colorimetric detection of total mercury level Atomic absorption spectrophotometry of

total mercury level Gas chromatograph with electron capture detector for organic mercury

Thin-layer chromatographic detection of organic mercury

Ultraviolet detector preceded by wet chemistry package

Pretreatment of Sample

Wet oxidation is used for the detection of the total mercury level, and solvent extraction is used for the detection of organic mercury.

Ranges 0.02÷0.5 ppm 0.1÷10 ppb 0.1÷10 ppb 0.02÷0.5 ppm from 0÷1 µg/l to 0÷100 ppm

Costs ($) 2,000÷5,000 (colorimetric spectrophotometers for laboratory applications)

~100,000 (depending on pretreatment of sample)

~35,000 (laboratory application) – 50,000 or more

Applications continuous on-line mercury monitors (industrial processes, including both effluent and quality controls in chlorine–alkali plants, quality controls of drinking water and of sulfuric acid, control of industrial sewage and

purification plants, monitoring the scrubber water in power plants and of waste incinerators)



Table 29: Moisture in Air: Humidity and Dew Point Types of Designs

Wet-dry bulb differential, psychrometer

Hair or synthetic fiber element

Cellulose element Thin-film capacitance (aluminum oxide or polymer)

Dunmore-type solution resistance element

Lithium chloride saturated salt dew-point sensor

Polystyrene surface resistivity (Pope cell)

Surface condensation on chilled surface (H1, detected optically using chilled mirror; H2, detected electrically)

Operating conditions

Operating temperature and pressure are usually limited to near atmospheric conditions although, with some designs (such as capacitance), the operating limits can be extended.

Ranges 10÷100% RH or –5÷50C 5÷100% RH for recorder; 20÷100% RH for dial

0÷100% RH 0÷100% RH –40÷10ºC (typical when used as dew-point sensor) down to –60ºC (with polymer sensors) 12÷99% RH or –64÷79ºC dew point

– – 15÷95% RH –73÷93ºC dew point or its equivalent (1 to 100% RH); high temperature units available up to 177C

Accuracy 2% RH 3÷5% RH 3÷5% RH 2÷3% RH standard 1% RH (up to 90% RH) and 2% RH (over 90% RH) is available (when used to detect dew point, an error of 2ºC is typical)

– 1C for dew points for –12÷38C 3÷5% RH 0.2÷0.4ºC dew point or 1% RH for 20÷90% RH

Costs ($) 75÷1,500 (sling psychrometer) 200 (laboratory psychrometer) 1,000 (digital, microprocessor- based psychrometer)

150 (125 mm diameter dial) 500÷600 (recording hygrothermograph)

~150 (125 mm dial or digital indicator) 750 (recorder)

300÷1,000 (portable, battery-operated digital indicator of RH and temperature) 1,000÷2,500 (benchtop meters) 250 (uncalibrated)÷500 (HVAC-quality duct or wall-mounted electronic transmitter) 1,500 (industrial-quality electronic transmitter) 2,500 (high-temperature transmitter)

500 (wall-mounted transmitter)

1,000÷2,000 (transmitter) 500÷750 (HVAC transmitters)

3,000 (portable, battery-operated unit) 8000 and up (bench or meteorological unit with continuous balance and aspirator) (3000÷5000, H1, cycled chilled-mirror unit)

Applications Sensors: weather monitoring or HVAC-related applications, although they also are used in industry Moisture analyzers: process industry applications and are less widely used for HVAC

Definitions Absorption—The taking in of a fluid to fill the cavities in a solid. Adsorption—The adhesion of a fluid in extremely thin layers to the surfaces of a solid. Dew point—Saturation temperature of a gas–water vapour mixture (the temperature at which water condensation occurs as a gas is cooled). Hygrometer—An apparatus that measures humidity. Hygroscopic material—A material with great affinity for moisture. Partial pressure—In a mixture of gases, the partial pressure of one component is the pressure of that component if it alone occupied the entire volume at the temperature of the mixture. Relative humidity—The ratio of the mole fraction of moisture in a gas mixture to the mole fraction of moisture in a saturated mixture at the same temperature and pressure. Alternatively, the ratio of the amount of moisture in a gas mixture to the amount of moisture in a saturated mixture at equal volume, temperature, and pressure (the ratio of how much water vapor is in the air vs. the maximum it could contain at the particular temperature).

Saturated solution—A solution that has reached the limit of solubility.

Table 30: Moisture in Gases and Liquids Types of Designs

Electrolytic hygrometer

Capacitance Impedance Piezoelectric Heat of adsorption

Infrared (IR)

Microwave Karl Fischer titrator (discussed under laboratory)

Drying oven (laboratory)

Dipole Cavity Ring Down

Neutron Calibrator

Ranges See “Summary of Moisture Analyzer Features” 10 ppm÷100% Usually in % 0.1÷100% ppt to ppm levels

0÷60% –

Accuracy 2÷5% FS 3% 3% 10% of actual reading or 2 ppm by volume, whichever is greater

– 2% FS For a 1÷15% moisture range, error is within 0.5%

0.5÷1% 0.5÷1% – – – –

Costs ($) 6,000÷15,000 (with sample system)

2,000÷10,000 (with thin-film probe) 2,000÷20,000 (flow-through bypass analyzer)

5,000÷40,000 – 10,000÷20,000 10,000÷15,000 20,000÷27,000 20.000÷40,000 15,000÷25,000 2,000÷5,000

Summary of Moisture Analyzer Features

Type Range Sample Phase Sample System Required Remarks

Electrolytic hygrometer 0÷2 to 0÷2000 ppm Clean gas Special sampling for liquids

Yes Sample flow must be constant

Change of capacitance 0÷10 to 0÷1000 ppm Clean gas or liquids * Sample temperature must be constant

Impedance type 0÷20,000 ppm Clean gas or liquids No, only for liquids Sample temperature of liquids must be constant

Piezoelectric type 0÷5 to 0÷25,000 ppm Clean gas only Yes –

Heat of absorption type 0÷10 to 0÷5000 ppm Clean gas or liquid Special sampling for liquids

Yes Sample flow must be constant

Infrared absorption Gas: 10.1÷100% Liquid: 6÷100%

Gas, liquids, and slurries ** –

Microwave absorption 0÷1 to 0÷70% Liquids, slurries, and pastes only No –

Note: *Available in probe form, but can be direct pipeline-mounted only if flow velocity is under 0.5 m/s. **Fiber-optic probe (FOP) designs can be direct pipeline-mounted without sampling.



Table 31: Moisture in Solids Types of Designs

Fast neutron moderation

Infrared Microwave Capacitance and dielectric constant sensors

Impedance, resistance

Nuclear magnetic resonance

Radio frequency absorption Karl Fischer titrator (laboratory)

Drying oven (laboratory)

Ranges 2÷80% From 0÷0.2% up to 1÷90% maximum

From 0÷1% to 0÷70%

4÷40% – – From 0÷35% to 0÷80% 10 ppm÷100% 0÷100%

Accuracy 0.2% if density is also measured and bound hydrogen is constant

0.5÷1% of calibrated range

For a 0÷15% range, the error is within 0.5%; on installations where nuclear density gauging is included, the error can be within 0.1%

0.5÷2% of full scale Error is under 0.05% moisture 5 ppm –

Costs ($) ~25,000 (if nuclear density gauge is also included)

10,000÷15,000 for reflectance units; higher for transmission systems operating at three frequencies to obtain thickness and density compensation

>15,000 (microwave only), or >25,000 (if nuclear density gauge is included)

~5,000 and up (industrial units) 1,000 (soil moisture detectors)

– – 7,000÷10,000 >10,000 ( if installation is included) 1,500÷2,000 (handheld meters) 5,000÷6,000 (computerized units for the laboratory) 7000÷13,000 (on-line RF or IR systems) 16,000÷36,000 (four-channel IR/RF) 40,000÷45,000 (on-line scanning,)

~10,000 5000 and up

Conclusions Of the methods available for moisture measurement in solids, the nuclear moisture gauge represents the most refined and accurate design. Other methods, such as infrared, microwave, and RF absorption, can also be used, particularly when the other process variables that affect the reading, such as temperature and particle size, are kept constant or are compensated for. Capacitance-type instruments can be used effectively on sheet paper, cardboard, and other materials where such factors as particle size and packing density are constant.

Table 32: Molecular Weight Types Membrane

osmometers Vapor pressure osmometers

Light-scattering photometers

Viscometers Liquid chromatographs, gel-permeation

End group determination Electron microscopy

Ultracentrifuge sedimentation

Applications Measurement of the liquid molecular weights of polymers and of other larger molecules

Design Pressure

Atmospheric

Design Temperature

150ºC

Element Material

Glass, Kel-F, gel-cellophane, stainless steel

Accuracy 5÷10%

Range Molecular weight of 50 and higher

Costs ($) ~10,000 ~10,000 ~10,000 35,000÷80,000 (Mooney viscometers, processability testers,

and rubber analyzers)

Over 50,000 ~100,000 3,000÷10,000

(laboratory centrifuges) Conclusions Of the methods available for the determination of polymer molecular weight, none is ideally suited for in-line measurement, but the techniques of gel permeation and viscometry can be applied using automated sampling systems. None of the

methods produces a direct output in terms of molecular weight. Sedimentation and diffusion methods are not very useful for process applications because of the time required to obtain a measurement. Gel-permeation chromatography, while its analysis time is in the order of 2 to 3 hr, provides a complete molecular weight distribution in addition to molecular weight averages. Automatic membrane osmometers are relatively fast, but their useful range is between 10,000 and 300,000 molecular weight. At the lower end, special membranes can be used to extend the range to about 5000 molecular weight. Vapor pressure osmometers complement the useful range of the membrane osmometer at the lower end of the scale. The operating range of these instruments is up to approximately 20,000 molecular weight. The analysis time and range of viscometers are comparable to those of the osmometers; however, their usefulness is limited to linear polymers. In terms of accuracy, range of application, and speed of analysis, the light-scattering photometer and the electron microscope offer the best choice. These instruments, however, are much more costly than other types, and their advantages rarely can justify the expense.



Table 33: Nitrate, Ammonia, and Total Nitrogen Ammonia Nitrite Nitrate Total nitrogen Nitrogen

Analysis Method

Dir

ect

Nessle

r

Dir

ect

ph

en

ate

Dis

tillati

on

-ti

trim

etr

ic

Dis

tillati

on

-Nessle

r

Dis

tillati

on

-ph

en

ate

Mic

roco

ulo

metr

ic

Gas

ch

rom

ato

gra

ph

ic

Ion

-sele

cti

ve

ele

ctr

od

es

Hyp

och

lori

te-

ch

em

ilu

min

escen

ce

Su

lfan

ilic

acid

m-p

hen

yle

ne

dia

min

e

Ph

en

old

isu

lfo

nic

acid

Ult

ravio

let

(UV

) ab

so

rpti

on

Bru

cin

e

Red

ucti

on

Sp

ecif

ic io

n-

ele

ctr

od

e

Ion

ch

rom

ato

gra

ph

y

Kje

ldah

l

Co

mb

usti

on

-ch

em

ilu

min

escen

ce

Gas c

hro

mato

gra

ph

-ch

em

ilu

min

escen

ce

Co

mb

usti

on

-ele

ctr

och

em

ical

dete

cto

r

Co

mb

usti

on

-th

erm

al

co

nd

ucti

vit

y

dete

cto

r

Pers

ulf

ate

dig

esti

on

-co

lori

mete

r

Costs ($)

35,0

00 (

an

au

toan

aly

zer

wit

h c

olo

rim

etr

ic

dete

cti

on

)

35,0

00 (

an

au

toan

aly

zer

wit

h c

olo

rim

etr

ic

dete

cti

on

)

–

–

–

–

–

350÷

700 (

sp

ecif

ic-i

on

ele

ctr

od

es)

–

35,0

00 (

an

au

toan

aly

zer

wit

h c

olo

rim

etr

ic

dete

cti

on

)

35,0

00 (

an

au

toan

aly

zer

wit

h c

olo

rim

etr

ic

dete

cti

on

)

35,0

00 (

an

au

toan

aly

zer

wit

h c

olo

rim

etr

ic

dete

cti

on

)

–

–

–

350÷

700 (

sp

ecif

ic-i

on

ele

ctr

od

es)

35,0

00 (

an

au

toan

aly

zer

wit

h c

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rim

etr

ic

dete

cti

on

)

–

9,5

00 (

a c

hem

ilu

min

escen

ce d

ete

cto

r m

od

ule

ad

ded

to

a T

OC

an

aly

zer

for

sim

ult

an

eo

us T

N a

nd

TO

C m

easu

rem

en

ts

30,5

00 (

a lab

ora

tory

TN

on

ly a

naly

zer)

65,0

00 (

an

on

lin

e T

N a

naly

zer)

20,0

00 (

ch

em

ilu

min

escen

ce d

ete

cto

rs f

or

gas c

hro

mato

gra

ph

s)

–

19,0

00÷

40,0

00

9(d

ep

en

din

g o

n t

yp

e o

f sam

ple

s)

for

a T

N a

naly

zer

based

th

erm

al

co

nd

ucti

vit

y d

ete

cti

on

0

–

Nitrogen cycle and Oxidation States of Nitrogen

Nitrogen cycle

Oxidation States of Nitrogen

Oxidation State Name Symbol

+5 nitrate ion NO31−

+3 nitrite ion NO21−

0 nitrogen N2

−1 hydroxyl amine NH2OH

−3 ammonia NH3

Environment issues

1, Because not all of the nitrogen fertilizer is retained in the soil long enough for its intended use, several environmental problems have arisen in recent years. Nitrogen compounds in streams and lakes result in an increased growth of algae, which depletes the available oxygen for oxygen-dependent organisms. The rapid eutrophication of lakes is at least partly a result of excess nitrogen compounds in the runoff. 2. Another process, termed nitrification , in which ammonium ion is oxidized to nitrate or nitrite, can also create problems in the aquatic environment by depleting the available oxygen. Ammonium ion in normally alkaline waters is in equilibrium with free ammonia, which is toxic to fish and other aquatic forms. Microorganisms decompose organic nitrogen compounds by a process called ammonification, which converts organic nitrogen compounds such as amino acids to ammonium ions. The ammonium ions created add to the problems described. 3. Another process that is part of the nitrogen cycle, denitrification, converts the nitrates or nitrites produced by nitrification into inert molecular nitrogen. Figure above shows the nitrogen cycle. Nitrate concentration, if higher than 45 mg/l in drinking water, causes an illness in infants called methemoglobinemia. The problems caused by nitrogen compounds in water have made it necessary to analyze for nitrogen in its many forms or oxidation states. The oxidation states of nitrogen are listed in table above.



Table 34: Nitrogen Oxide Analyzers Analysis Methods Infrared Ultraviolet Chemiluminescent Colorimetric Electrochemical Coulometric Gas chromatography

Reference Method Colorimetric, applied to integrated samples collected in alkaline solution

Ranges 0÷500 ppm to 0÷10% 0÷100 ppm to 0÷100% 0÷50 ppb to 0÷10,000 ppm Down to ppb 0÷500 ppm to 0÷2500 ppm – Down to ppb

Accuracy Generally 1÷2% of span, but some microprocessor-based electrochemical designs can be accurate within 2% of reading, and some chemiluminescent units are accurate within 0.5% of span.

Costs ($) Note: The installation and the upkeep costs are normally larger than the first costs of purchasing.

4,000÷5,000 (single-beam portable or laboratory units) 8,000 (an industrial NDIR) 25,000÷27,000 (a multi-gas analyzer pulling in up to five gases from 50 m distance) 75,000÷125,000 (FTIR)

2,500÷5,000 (laboratory spectrophotometers) 20,000 (industrial units)

~10,000÷20,000 ~50,000 >750 (pocket-sized personal monitors) >1,500 (remote sensor heads) >5,000 (on-site monitors with data loggers) 6,000÷8,000 (stack gas analyzer with printer, auto calibration, and probe)

– 50,000÷100,000 (Installed cost)

Nitrogen Oxide Analyzers Type

– – – Griess–Saltzman

Jacobs–Hochheiser – – –

Nitrogen Oxide Analyzers Advantages

– – Dry gases only, sensitive photometry, continuous analysis

Precise, thoroughly tested, widely used, continuous analysis Precise, stable after collection

Simple apparatus, continuous analysis Simple apparatus, continuous analysis

Specific, frequent analysis

Nitrogen Oxide Analyzers Disadvantages

– – Requires ozone generator NO2 catalytic reduction.

Short life of collected sample, sensitive reagents, NO oxidation required. Not adapted to continuous analysis, sensitive reagents, NO oxidation required.

Sensitivity not high, NO oxidation required. Sensitive to other oxidants, NO oxidation required.

Not a developed instrument, expensive and complex.

Conclusions The most widely used conventional method of ambient air analysis is colorimetric. It is most often based on the use of the Griess–Saltzman reagent (a diazotization method). This is a fairly precise and dependable method but requires a great deal of attention. The colorimetric method is specific for nitrogen dioxide. To analyze for nitric oxide, an oxidation step is required. Of various oxidizer columns, the most commonly used is the permanganate one, but none is completely satisfactory. It is important to calibrate it over a range of nitric oxide concentrations and at various humidity levels. The chemiluminescent method utilizes the reaction between ozone and nitric oxide. This is a dry gas method requiring an ozone generator and compressed gas. In the chemiluminescent method, a catalytic reduction of nitrogen dioxide to nitric oxide is required. For industrial applications, the most often used analyzers are the nondispersive infrared, ultraviolet, and electrochemical types. The chemiluminescent and gas chromatographic techniques are less frequently used.

Table 35: Odor Detection Methods of Detection Organoleptic Instruments, such as chromatographic, mass spectrographic, thermal conductivity, catalytic

combustion, semiconductor, flame ionization, photoionization Electronic nose

Sensitivity of Detection ~0.2 ppb ~10÷200 ppb ppt to ppb, depending on chemical

Costs ($) ~100,000 (chromatograph installed with accessories) 15,000 (portable chromatograph with electrochemical sensor) ~100,000 (mass spectrograph) 3,400÷6,800 (photoionization, portable) ~1,200 (solid state gas hydrocarbon portable) 700÷100,000 (polymer, MOV, fiber optic, calorimetric, amperometric, gravimetric)

The Relative Odor Intensity of Different Chemicals

Odor Intensity Abbreviation Name (Formula) (W)

EM Ethyl mercaptan ethanethiol (CH3H) 1.08

DMS Dimethyl sulfide methylsulfide ((CH3)2S) 1.0

IPM Iso propyl mercaptan 20-propanethiol CH3CHSHCH3) 0.88

MES Methyl ethyl sulfide methyl thioethane ((CH3)2CH2S) 0.66

NPM Normal propyl mercaptan 1-propanethiol ((CH3)CH2CH2SH) 0.85

TBM Tertiary butyl mercaptan 2-methyl 2-propanethiol ((CH3)3CSH) 1.00 (ref)

SBM Secondary butyl mercaptan 1-methyl 1-propanethiol ((CH3)2CH2CHSH) 1.99

DES Diethyl sulfide ethyl sulfide (C2H5)2S) 0.22

Thiophane Thiophane tetrahydrothiophene (C4H8S) 1.63

EIS Ethyl isopropyl sulfide (–) 0.07

Note: Odor is a sensation associated with smell, which can be hard to quantify. The same quantities of different materials cause different odor intensities. The unit of odor intensity is based on the odor of tertiary butyl mercaptan (TBM; W = 1.0). Using that reference, H2S, for example, has an odor intensity of 0.08 or 8% of TBMs. Most odorant substances contain sulfur. Table above lists a number of odorant substances and their relative odor intensities (W).

Applications This technology allows the analyzers to be small—at least desktop size and, in some cases, easily handheld. There are indications that credit card size devices will eventually be developed. A sensor can be designed to be as specific or as broad in application as desired. There are many possible applications in industrial and commercial safety, drug interdiction and enforcement, explosive detection, pharmaceuticals, medical, food and beverage, perfumes, breweries, wineries, etc. Anywhere an odor can be used to detect the presence or even absence of a substance, these electronic noses can be used. The cycle time is typically a few seconds but can be longer, depending on the chemical and the vapor state. Temperature dramatically affects the vaporization of most chemicals, thereby reducing the amount of chemicals to cause an odor. When a sensor/analyzer is used for batch applications, there is an additional time required to purge and clear the sensor array, allowing it to return to a baseline state. One manufacturer has recently introduced a sensor and analyzer to detect the odor of hydrocarbons in water.



Table 36: Oil in or on Water Types of Designs Reflected light oil slick detector (on-

off) Capacitance: available in probe form for interface detection or in a flow-through design or in a floating plate configuration for measuring the thickness of oil

Ultraviolet (UV) Microwave (radio frequency): available as an interface probe, as a tape-operated tank profiler, or as an oil in water content detector

Conductivity probes for interface detection Nuclear for interface detection

Range Generally from 0÷50 ppm to 0÷100%

Flow-through dual-concentric detector from 5÷15% water in oil

0÷10 ppm to 0÷150 ppm oil in water Oil content detectable from 0÷100% – –

Accuracy Generally from 1÷5% of full scale The flow-through dual-concentric detector has a sensitivity of about 0.05÷0.1% water

0.1 ppm for a 0÷10 ppm range Interface is detected to 5%; tank profile, to 1% or 3 cm, and water concentration, to 0.1%

– –

Costs ($) See Annex B. See Annex B. 12,000÷20,000 (for dual-wavelength unit with auto-zero and 0÷10 ppm to 0÷150 ppm range

– See Annex B and Table 14. –

Conclusions The on-off oil-on-water detector is capable of measuring as little as a few drops of petroleum floating on the surface of water, thus making it possible to detect those oil pollution levels that are visible to the human eye. It therefore serves a useful purpose as an alarm device downstream of plant outfalls and especially during and immediately after oil loading and unloading operations from tankers and tank trucks. This device presents the maintenance problems usually associated with optical measurements, which is that windows must be kept clean. The air column between the water surface and the window does reduce fouling due to splashing, but window cleanliness must be maintained for maximum sensitivity. The oil-thickness device, being non-optical, requires less maintenance. Because both devices can detect the absence or presence of oil slicks, they might also find application as oil spill monitors after oil transfer operations. Floating on the surface of wastewater storage sumps or lagoons, the output of the oil thickness monitor can be used to start and stop oil reclamation equipment. These devices cannot be calibrated for a specific oil fraction, but just respond to any floating hydrocarbon. The oil-in-water devices are optical, and even the falling stream types require clean windows, although they are less subject to fouling than the sample chamber types. They must be calibrated for a specific type of oil, and other oil fractions will introduce errors. They were originally developed to monitor engine oil contamination in boiler feed water and condensate, which can be introduced by steam-driven feed water pumps. These devices detect the presence of a specific hydrocarbon fraction in well segregated waste streams. Where particle size is expected to exceed 5 µm, sample preparation prior to the UV analysis is necessary. Use of a high-shear mixer such as a blender has been found to produce a well dispersed suspension suitable for measurement.

Table 37: Open Path Spectrophotometry (UV, IR, FT-IR) Types of Devices FTIR Combustibles detection Tunable diode laser UV

Applications Ambient air or fence-line monitoring for the detection of toxic or hazardous vapors for emissions monitoring as well as combustible vapors in personnel safety applications.

Costs ($) 86,000 (for minimal instrument configuration) 150,000 (typical installed cost)

5,000÷7,000 35,000÷75,000 (depending on configuration) 25,000

The regimes of operation in the electromagnetic spectrum for various path sensors. Note: (1) A 300 K (27 °C) blackbody emission spectrum is superimposed on the diagram. Note that atmospheric absorption limits the range of FTIR measurements to two atmospheric transmission windows. (2) OP-TDLAS = Open Path-Tunable Diode Laser Spectrometry (3) OP-FTIR = Open Path-Fourier Transform Infra Red (4) OP-HC = Open Path-Hydrocarbon Combustibles (5) OP-UV = Open Path-Ultra Violet

Typical applications Open path monitoring is used for analytical measurements in remote and inaccessible locations. The technique is also used for perimeter monitoring of structures and facilities. Such monitoring is either to detect the

release of low levels of toxic and hazardous vapors, or it is to signal the releases of combustible hydrocarbons at relatively much higher levels. The use of open path monitoring is driven by either the need for probing an area without physical intrusion or by the need to monitor an area that is larger than one that can be cost effectively monitored with a requisite number of point detectors. Open path monitoring is a subset of the techniques collectively called long path monitoring. Long path monitoring includes the use of multipass reflection cells to cover distances as great as hundreds of meters and achieve high detection sensitivity. The two general uses of open path vapor detection, toxic and combustible detection, have resulted in instruments that have evolved specifically for each application. Open path toxic gas detection is generally used for very low-level detection—often in fence-line monitoring roles for estimation of emissions from a facility. There are many more open path combustible hydrocarbon (OP-HC) detectors in use than there are toxic detectors. In a petrochemical plant, there can be as many as 150 OPHC detectors, but only about half a dozen or fewer open path toxic detectors. Combustible detection requires much less instrument sensitivity, but instruments are highly engineered to provide much more protection against false alarms and to deliver high availability in excess of 99.9%. Immunity to false alarms is very important, because, when an alarm is actuated, executive action is frequently taken. Nondispersive infrared (NDIR) spectroscopy is most often used in OP-HC detectors. In applications in which FTIR does not have sufficient sensitivity, open path ultraviolet (OP-UV) spectroscopy is frequently employed. This methodology can be used for applications involving the detection of homonuclear diatomic molecules (chlorine, bromine, etc.), which have no infrared absorption, or of molecules that absorb only weakly in the IR region, such as benzene, sulfur dioxide, and nitrogen oxides. Because low-cost, highly reliable, solid state diode lasers have been developed and became available for high-volume telecommunications applications, a new class of open path detectors has been developed and applied to a subset of toxic measurement applications. Instruments in this category utilize the ability of the diode laser to scan over very short wavelength intervals. This method of measurement is referred to as open path tuneable diode-laser absorption spectroscopy (OP-TDLAS).



Table 38: Oxidation-Reduction Potential (ORP) Design Pressure Vacuum to 10.6 barg is standard; special assemblies are available for up to 35 barg

Design Temperatures Generally from –5÷100ºC

Materials of Construction Mounting hardware available in stainless steel, Hastelloy, titanium, PVC, CPVC, polyethylene, polypropylene, epoxy, polyphenylene sulfide, Teflon, and various elastomer materials; electrodes available in platinum or gold.

Assemblies Submersion, insertion, flow-through, and retractable

Cleaners Ultrasonic, water or chemical jet washer, brushes

Range Any span between –2000 mV and +2000 mV

Accuracy Typically ±10 mV and a function of the condition of the noble metal electrode and of reference electrode drift; repeatability about ±3 mV

Costs ($) 100÷500 (electrodes) 300÷1,000 (portable or bench-top laboratory display and control units) 500÷2,000 (transmitters) 500÷2,000 (cleaners)

Applications 1. In ore leaching, metal is leached from the ore and converted to the desired state for further processing. 2. Toxic cyanides are oxidized to harmless reaction products in an oxidation-reduction reaction as part of the process to remove toxic heavy metals. 3. In the pulp and paper industry, pulp is bleached with a variety of oxidants under ORP measurement and control. 4. Hexavalent chromium is reduced to the trivalent oxidation state as part of the process for removal of toxic chromium from metal finishing or from cooling tower blow-down wastewaters. 5. The manufacture of chlorine bleaches is controlled by ORP. 6. In sanitary wastewater treatment, ORP is used to control the addition of an oxidant for odor control.

Reduction Potentials of Solution in ORP Measurement

Reduction E°, Volts

O3+2H3O++2e−=O2+3H2O +2.070

Cr2O72−

+14H3O++6e−=2Cr

3++21H2O +1.330

ClO−+H2O+2e

−=Cl

−+2OH

− +0.890

Fe3+

+e−=Fe

2+ +0.770

Ag/AgCl electrode 4 M KCl +0.199

2H3O++2e

−=H2+2H2O 0.000

Zn2+

+2e−=Zn −0.763

CNO−+H2O+2e

−=CN

−+2OH

− −0.970

Na++e

−=Na −2.711

Table 39: Oxygen in Gases Design Types 1. Deflection-type

paramagnetic, dynamic dumbbell

2. Thermal-type paramagnetic

3. Dual-gas (differential pressure) paramagnetic

4. Catalytic combustion 5. Low-temperature electrochemical (galvanic, coulometric, polarographic)

6. Zirconium oxide, voltage-mode high-temperature electrochemical

7. Zirconium oxide, current-mode high-temperature electrochemical

8. Alarm, pocket-size, battery-operated

9. NIR spectroscopy

Sample Requirement All require a sampling system except the 6th, 7th and 9th types, which can be inserted into the process as probes or utilize fiber optics process interfaces.

Sample Pressure and Flow

Generally, near atmospheric pressures and low flow rates in the range of a few SCCM to a few SCFH

Materials of Construction Most are suitable for corrosive service, and the 6th, 7th and 9th types are also suitable for high-temperature service.

Speeds of Response Most will reach 90% of full scale in <1 min; response times of the 6th and 7th types are in milliseconds and the last one is in seconds.

Operating Temperatures Most designs are suited for 93°C service. The 6th and 7th types can operate at up to 621°C with stainless steel, up to 1204°C with mullite, and up to 1593°C with silicon carbide materials.

Ranges 0÷25% 0÷25% 0÷100% 0÷2000 ppm From 0÷1 ppm up to 0÷25%

Most often used for 0÷5%, 0÷10%, and 0÷25%, but can be obtained with ranges as wide as 1 ppm÷20% or 0.5%÷100%

Most often used for 0÷5%, 0÷10%, and 0÷25%, but can be obtained with ranges as wide as 1 ppm÷20% or 0.5%÷100%

Usually set to alarm at about 18% oxygen concentration

From 100 ppm, typically 0÷2% or 0÷100% range

Accuracy Error 0.02% oxygen between 98÷100% oxygen

Generally 1÷2% of full scale

Generally 1%÷2% of full scale

5% of span Generally 1%÷2% of full scale





Costs ($) – 6,000÷10,000 6,000÷10,000 5,000 >1,200 (portable monitoring units) 5,000÷20,000 (industrial analyzers with spans in the ppm)

5,000÷15,000 5,000÷15,000 500÷1,000 (portable, battery-operated, pocket-size, low-oxygen alarms)

20,000÷25,000

The Magnetic Susceptibility of Different Gases, with Oxygen Given as 100

Acetylene (C2H2) −0.24 Hydrogen (H2) +0.24

Ammonia (NH3) −0.26 Methane (CH4) −0.2

Argon (Ar) −0.22 Nitric oxide (NO) +43.0

Carbon dioxide (CO2) −0.27 Nitrogen (N2) 0.0

Carbon monoxide (CO) +0.01 Nitrogen dioxide (NO2) +28.0

Ethylene (C2H4) −0.26 Oxygen (O2) +100.0

Hexane (normal) (C6H14) −1.7



Table 40: Oxygen in Liquids (Dissolved Oxygen) Types Polarographic Galvanic Coulometric Multiple-anode Multiple-anode Fluorescence

Operating Pressure Up to 3.5 barg or submersion depths of up 8.3 m

Operating Temperature Range 0 to 50ºC; special designs up to 80ºC

Flow Velocity at Sensing Membrane Preferably in excess of 0.3 m/s; some can operate down to 0.06 m/s

Materials of Construction Typical material for sensor housing: PVC or stainless steel; possible electrode materials: platinum, gold, silver, zinc, lead, cadmium, and copper; for membrane assembly, ABS plastic or stainless steel mesh-reinforced silicone and/or Teflon membrane

Speed of Response 90% in 30 sec; 98% in 60 sec

Ranges Common ranges are 0÷5, 0÷10, 0÷15, and 0÷20 ppm; special units are available with ranges up to 0÷150 ppm or down to the 0÷20 ppb range used on boiler feedwater applications. Systems can also be calibrated in partial pressure units.

Accuracy Generally, ±1÷±2% of span; industrial transmitter errors are generally within 0.02 ppm over a 0÷20 ppm range. Thallium cells are available with a 0÷10 ppb range and can read the dissolved oxygen (DO) within an error of 0.5 ppb.

Costs ($) 500÷2,000 (portable, battery-operated, 1.5÷2% FS units that also read temperature) 250÷1,000 (replacement probes) 1,000÷2,000 (1% FS, microprocessor based portable benchtop units for laboratory or plant service) 2,000÷3,500 (industrial-quality (0.02 ppm error limit) DO probe and 4 to 20 mA transmitter) 500÷2,000 (cleaning assemblies)

Application Considerations The applications in which dissolved oxygen sensors are used include biopharmaceutical, water and wastewater, food and beverage, and chemical processing. Each application category dictates slightly different requirements for the sensor and transmitter. Biopharmaceutical applications require that the sensor body be of a hygienic design to allow for cleanability and to resist clean-in-place and sterilize-in-place conditions. Therefore, the sensor bodies are usually polished stainless steel and have no exposed grooves or crevices where matter can accumulate. Additionally, membranes usually have an outer layer of Teflon to resist the buildup of coating. In contrast, in wastewater applications, the specifications are less stringent, so sensors are usually constructed from polymer materials, have lower temperature and pressure ratings, and are less resistant chemically. Similar to biopharmaceutical applications, food and beverage usage usually requires that the sensor be of a hygienic design. However, it does not necessarily need to withstand sterilization conditions. Often, in food and beverage applications, the sensor is exposed only to temperatures that are high enough to pasteurize the process liquid. Chemical process applications require sensor characteristics similar to those for biopharmaceutical and food and beverage applications. In these applications, too, the materials used must withstand higher temperatures and pressures than polymer materials can provide and must have good chemical resistance characteristics. For hazardous area applications, an intrinsically safe sensor must be considered, and manufacturers are usually able to supply intrinsic-safety related information.

Table 41: Ozone in Gas

Ultraviolet light absorption Methods of Detection

Single-beam Double-beam

Amperometric Thin-film semiconductor Acoustic

Sample Flow Rate 0.5÷5 l/min

Ranges 0÷10 ppm by volume (low concentration); 0÷25% by weight (high concentration)

Sensitivity of Reading 0.001 ppm by volume (low concentration); 0.001% by weight (high concentration)

Accuracy (% of Reading) 1% 1% 1÷5% 10% or more 0.5%

Cost ($) 3,500÷7,000 3,000÷15,000 1,200÷8,000 400÷1,500 1,500

Applications Gas phase ozone monitoring and analysis is most frequently done on air or oxygen streams, serving one of the following purposes: 1. Monitoring atmospheric ozone concentrations 2. Monitoring and controlling the ozone concentration in the output of ozone generators 3. Monitoring ozone concentrations in the off-gas streams of ozone treatment systems 4. Monitoring ambient ozone concentration in ozone generator rooms

Table 42: Ozone in Water

Amperometric Methods of Detection*

With bare

electrodes With membrane

Stripping and gas phase detection

Ultraviolet absorption Colorimetric

Sample Requirements 100÷500 cc/min 100÷500 cc/min 1.5 l/min 100÷500 cc/min (no tolerance for the presence of suspended matter)

100÷500 cc/min (no tolerance for the presence of suspended matter)

Sensitivity (ppm=mg/l 0.01 ppm 0.01 ppm 0.001 ppm 0.001 ppm 0.05 ppm

Ranges (ppmmg/l) 1 ppb 5 ppb÷1% 1% 3% 1.5%

Costs ($) 8,000 2,500÷8,000 5,500÷8,500 3,000÷5,000 300÷3,000

Applications Ozone monitoring is used for: 1. dissolved ozone measurement in water treatment 2. in ozone treatment of wastewater 3. ozone contactor monitoring, 4. industrial ozone treatment process monitoring.

Note: * =: In the past, oxidation-reduction potential (ORP) analyzers have also been used, but now they are only employed in such noncritical installations as in swimming pools, where they signal the presence or absence of ozone.



Table 43: Particulates, Opacity, Dust, and Smoke

Sample and Monitor Types

Hig

h-v

olu

me

sam

ple

r

Dic

ho

tom

ou

s

sam

ple

r

Tap

e s

am

ple

r

Man

ual st

ack

sam

ple

r

Pie

zoele

ctr

ic c

rysta

l m

ass b

ala

nce

Imp

acti

on

devic

es

Rad

iom

etr

ic d

evic

es

Ch

arg

e

tran

sfe

r

Su

rface

ion

izati

on

Lig

ht

att

en

uati

on

/tra

nsm

isso

mete

r

Lig

ht

scatt

eri

ng

Vis

ual o

bserv

ati

on

Rem

ote

sen

sin

g

Sta

ck g

as

mo

nit

ors

Sam

plin

g

pro

bes

Potential Applications – Particle sizing

– – – Particle sizing

Fire/smoke detection

– – Visibility Fire/smoke detection Particle sizing

Visibility Particle sizing

Visibility – –

Type of Sample and Installation

Extractive Ambient air



Extractive Ambient air Flue/stack gas


Extractive Ambient air Flue/stack gas

In situ Extractive Ambient air Flue/stack gas

In situ Flue/stack gas


In situ Ambient air Flue/stack gas




–

Reference Methods EPA 40 CFR 50 Appendix B

– ANSI/ASTM D1704–78

EPA 40 CFR 60 Appendix A, Method 5 ANSI/ASTM D2928–71 ANSI/ASTM D3685–78

– – – – – EPA 40 CFR 60 Appendix B, Perf Spec 1

– EPA 40 CFR 60 Appendix A, Method 9 ANSI/ASTM D3211–79

– –

Standard Smoke Density Ranges

0÷18.7%, 0÷33.9%, 0÷64.5%, 0÷87.4%, and 0÷98.4% (in units of % opacity) 0÷0.09, 0÷0.18, 0÷0.45, 0÷0.9, and 0÷1.8 (in units of optical density)

Accuracy of Smoke Density Transmissometers

±3% of range

Costs ($) <2,500 2,500÷6,500 2,500÷6,500 2,500÷6,500 2,500÷6,500 1,200÷5,000 5,000÷20,000 <2,500 5,000÷20,000 5,000÷20,000 5,000÷100,000 5,000÷100,000 5,000÷7,000 (portable O2, O, Ox, and SO2detection packages) 25,000÷35,000 (a package to continuously monitor the emissions of CO, CO2, SO2,NO, NOx, O2, and opacity)

1,300÷2,500 (probes only in 1÷3-m lengths with glass, quartz, or stainless steel lining) 10,000÷15,000 (a complete EPA (Reference Method 5) particulate-sampling system)

Conclusions Particulate-monitoring methods have been developed that achieve high standards of accuracy and reliability. Under the impetus of the EPA, such methods have become widely used in the United States. Future developments are anticipated in the particle sizing area as regulatory agencies become less concerned with the visual effects of smoke and more concerned with its health effects. Visual effects, highway and airport visibility in particular, will continue to be of substantial interest as will the conditions of scenic vistas and parks.



Table 44: Particle Size and Distribution Monitors Measurement Technique

Optical imaging Electron imaging Image analysis (with A or B)

Optical diffraction and laser scattering

Electrical resistance change

Sieving Sedimentation (photo or x-ray)

Ultrasonic attenuation Bulk property—absorption, permeability

Aerodynamic time of flight

Over 1.0µm 0.006÷0.01µm resolution

– Laser scattering analyzer range covers from 0.02÷2000µm for air-suspended particles. For water-suspended particles, the minimum size is around 1µm.

Over 0.5µm Usually >75µm but, with careful design, down to a few microns

1÷100µm 25÷600µm – – Ranges

For continuous airborne particle counters: 0÷10 million or 0÷1 billion particles/cubic foot; ranges are selectable to count particles that are larger than 0.3, 0.5, 1, 3,5, or 10µm. Sensitivity can be as high as 1 mg/m3, and particles down to microns are detected. For on-stream particle-size monitors (dry powders or slurries), particle-size distribution data can be measured between 2÷300µm.

Accuracy 5% (particle size distribution)

Costs ($) 6,000÷18,000 25,000÷100,000 40,000÷80,000 15,000÷40,000 6,000÷18,000 1,000÷8,000 6,000÷18,000 6,000 (regular sludge densitometer) up to 50,000 (size distribution detection with referee method)

1,000÷8,000 –

Application Objectives Accurate determination of particle size and distribution is critical in many industrial processes, such as grinding, agglomeration, crystallization, and emulsification. Objectives may include improving final product quality, as in ceramics, paints, and pigments; improving final product performance, as in abrasives and catalysts; improving process efficiency, as in crystallization and wastewater treatment; or minimizing energy consumption, as in grinding of ore for subsequent processing. In many processes, more than one of these objectives may be involved. This table discusses the range of particle size measurement from approximately 0.01 to about 1000 μm. The goal of these measurements is determining the quality of material in a process rather than the detection of contaminants in an otherwise particle-free stream. The performance characteristics noted above are attainable from standard commercial instruments.



Table 45: pH Measurement Standard Design Pressures Vacuum to 7 bars; special assemblies to 35 bars

Standard Design Temperatures

−5÷100°C (generally) −30÷130°C (sterilizable) −5÷140°C (Glasteel, (<5 pH))

Materials of Construction Electrode hardware: stainless steel, monel, Hastelloy, titanium, epoxy, Kynar, halar, polyvinyl chloride, chlorinated polyvinyl chloride, polyethylene, polypropylene, polyphenylene sulfide, Ryton, Teflon, various elastomer materials

Assemblies Flow-through, submersion, insertion, and retractable

Cleaners Ultrasonic, jet washer (chemical and water), and brush

Accuracy 0.02 pH (electrodes) 0.01 pH (lab meters and displays) 0.02 mA (transmitters) 0.2 pH (installation effects)

Range 0÷14 pH

Costs ($) 100÷500 (electrodes) 2,000 (Glassteel) 200÷800 (lab meters) 500÷2,000 (transmitters) 200÷1,000 (assemblies) 500÷2,000 or more (automatic cleaners) 15,000÷25,000 (fiber-optic unit)

Applications pH measurement is used to reduce sodium hydroxide addition to its bare minimum and still ensure complete use of sodium bisulfite. In addition, pH measurement is used to correct the inference of hypochlorite concentration from an oxidation-reduction potential (ORP) measurement. Since ORP curves drastically shift with pH, the use of ORP to infer the concentration of oxidizing or reducing species must be accompanied by an accurate pH measurement. Biological reactors use acids and bases to supply food to or neutralize the waste products of organisms. Cells are extremely sensitive to pH fluctuations. Genetically engineered bacteria tend to be weak and need particularly tight pH control. Thus, pH is critical to cell growth rate, enzyme reactions, and extraction of intercellular products. The sensitivity of cells to pH has even wider significance in that any food, drink, or drug ingested or injected, and any waste discharged to the environment, must have pH specifications to prevent damage to living matter and ecological systems. Stricter environmental regulations have increased the number and importance of pH measurements. Some environmental regulations have instantaneous limits on pH. An excursion outside the acceptable range for a fraction of a second can be a recordable violation. The pH measurement system must be designed to prevent violation indications from spurious readings due to installation effects. For most discharges, the acceptable range lies between 6 and 9 pH. To ensure that a surface impoundment can be declassified (nonhazardous), the pH of all entering streams must always be between 2 and 12.5 pH. Whereas materials of construction are generally less sensitive to pH than are living cells, a range of pH must be maintained to prevent corrosion of metals or disintegration of plastics. Intermediate pH control is often needed to prevent damage to vessels, piping, and instrumentation.

The logarithmic nature of pH

Conclusion The pH sensor should be chosen to meet the pH range of the application. The mounting method should be chosen to make the sensor easily accessible for maintenance and calibration. Most pH applications that involve water and dilute solutions at near ambient

temperature are straightforward and pose few problems. Special care should be taken with applications involving components that can poison the reference or foul the sensor, nonaqueous solvents, low conductivity, and extremes of temperature and pressure. In applications where the nominal pH is expected to be at the high or low limits of the 0 to 14 pH range, a conductivity measurement should be considered as an alternative measurement of acid and base concentration. It should be remembered that the pH of solutions can change with temperature. This is particularly the case with solutions that have a neutral or basic pH. It never hurts to consult several sensor suppliers as to the suitability of their various designs to a particular process application.

Relative Performance of Different pH Probe Designs Considering a Number of Performance Criteria



Table 46: Phosphorus Analyzer Methods of Detection Colorimetric Flame photometric Chromatographic

Operating Pressure Atmospheric

Materials of Construction Most analyzers can be obtained with wetted parts made out of stainless steel, glass, or Teflon

Accuracy (of full scale) 2÷3%

Analysis Time From a fraction of a minute to 15 min

From 0÷5 ppm to 0÷20 ppm From 1÷100 ppm – Ranges

The overall capability of measurement for all types is from 0÷10 ppb to 0÷100 ppm

Costs ($) 10,000÷25,000 (laboratory units) 25,000÷100,000 (industrial installations with sampling system included) ~2,500 (vane-type filters for sewage applications)

Applications The principal application of phosphorus analyzers is in the control of phosphate removal in sewage treatment plants. By knowing the flow rate and the phosphorus content of raw sewage, the required optimal quantities of chemical additives can be determined. In addition, a measurement of the phosphorus remaining after treatment may be desired. Phosphorus occurs in wastewater almost entirely in the form of phosphates, including orthophosphates, condensed phosphates (pyrophosphate, metaphosphate, and polyphosphate), and as organically bound phosphates. The various methods of phosphorus detection do not all respond to the total phosphorus present. Other applications are those specific to the control of phosphate addition to high-pressure boiler water as a corrosion inhibitor, and to the measurement of elemental phosphorus in the effluent from a plant that extracts phosphorus from ore.

Table 47: Physical Properties Analyzers—ASTM Methods Analyzer Type

Dis

tillati

on

an

aly

zer

Vacu

um

d

isti

llati

on

an

aly

zer

Ho

rizo

nta

l sti

ll

dis

tillati

on

an

aly

zer

Sim

ula

ted

d

isti

llati

on

by

gas

ch

rom

ato

gra

ph

y

Air

-satu

rate

d

vap

or

pre

ssu

re

an

aly

zer—

co

nti

nu

ou

s

Air

-satu

rate

d

vap

or

pre

ssu

re

an

aly

zer—

cyclic

Dyn

am

ic

vap

or

pre

ssu

re

an

aly

zer

Co

nti

nu

ou

s

vap

or—

liq

uid

ra

tio

an

aly

zer

Dif

fere

nti

al-

pre

ssu

re p

ou

r p

oin

ter

Vis

co

us-d

rag

p

ou

r p

oin

ter

Op

tical-

clo

ud

p

oin

t an

aly

zer

Fre

eze

-po

int

an

aly

zer

Lo

w-

tem

pera

ture

fl

ash

-po

inte

r an

aly

zer

Hig

h-

tem

pera

ture

fl

ash

-po

int

an

aly

zer

Octa

ne e

ng

ine

co

mp

ara

tor

an

aly

zer

Reacto

r-tu

be

co

nti

nu

ou

s

octa

ne

an

aly

zer

Near-

infr

are

d

infe

ren

tial

measu

rem

en

ts

Potential Applications

1. Crude fractions 2. Gasoline components /product

1. Crude fractions 2. Gasoline components/ product



1. Gasoline components/ product




1. Crude fractions 2. Lube oils

1. Crude fractions 2. Lube oils

1. Crude fractions 2. Diesel

1. Crude fractions 2. Jet or kerosene

1. Crude fractions 2. Diesel 3. Jet or kerosene

1. Lube oils 1. Gasoline components/ product


–

Reference Methods

ASTM D86 ASTM D1160 ASTM D86 ASTM D2887/D3710

ASTM D4953–90

ASTM D4953–90

ASTM D4953–90 ASTM D1267

ASTM D2533 ASTM D97 ASTM D97 ASTM D2500 ASTM D2386 ASTM D56/D93

ASTM D56/D93

ASTM D2699/D2700

ASTM D2699/D2700

–

Costs ($) 40,000 56,000 31,000 40,000 38,000 28,000 26,000÷ 35,000

85,000 37,000 41,000 28,000 33,000 44,000 41,000 220,000 86,000 100,000

Orientation Table for Physical Properties Analyzers

Analyzer Type Range Repeatability ( + / −) Flow Rate (LPH) Pressure (kPa) Temperature (C) Cycle Time (minutes)

Distillation 5÷95% 38÷343ºC

1% sample boiling range

4.5 138÷1,035 17°C below IBP 5

Vacuum 343÷538ºC 1% sample Boiling range

8.7 345÷1724 82°C max 16

Horizontal Still 5÷95% 65÷343ºC

Equal or better than ASTM 1.5 35÷700 22ºC lower than IBP 2

Distillation

Simulated Distillation 2÷98% –17÷538ºC

2÷7ºC 15 (sample inject) 35÷1,035 Below expected IBP 10÷30

Air-saturated Continuous 2÷19 psia 0.1 psia 6 69÷690 10÷43ºC 2

Air-saturated Cyclic 0÷20 psia 0.05 psia Bypass flow – – 9

Vapor Pressure

Dynamic 0÷20 psia 0÷200 psia

Equal to or better than ASTM 38÷190 520÷3,450 21÷49ºC 0.75

Vapor/Liquid Continuous 10÷30 V/L to 66ºC 0.5 V/L 7.6÷15.1 350÷1,050 Normal Blending Range 3

Differential Pressure –59±10°C 2°C 7.6 <138 11°C above pour point 5÷15 Pour Point

Viscous Drag –31±38°C <1°C 0.6÷6 100 75°C max 30÷42

Cloud Point Optical –25±15°C 0.6°C 11.3÷18.9 1,724 11°C above pour point 2

Freeze Point Aviation Fuels –65÷ –10ºC 0.6ºC 11.3÷18.9 1,724 10÷50ºC 3

Low Temperature 10÷50ºC 1ºC 13.2 6,895 139ºC max above flash point 1÷7 Flash Point

High Temperature 60÷316°C 1.5°C 3.8 69÷863 28°C below flash point 1÷5

Comparator Engine ASTM Specs ASTM Specs ASTM Specs ASTM Specs ASTM Specs ASTM Specs Octane

Reactor Tube 2 Octane Numbers 0.1 RON 0.06 350÷3,500) 38°C 2



Table 48: Raman Analyzers Process Fluids Liquids, powders, slurries, emulsions (gases)

Operating Pressure Analyzer (ambient), sample interface (3,000 PSI)

Operating Temperature Analyzer (0÷50ºC), sample interface (350ºC)

Humidity Limitations 20÷100% noncondensing

Calibration Transfer Intra-analyzer transfer after maintenance and transfer between analyzers

Sample Interface Invasive, noninvasive

Wetted Material Stainless steel, titanium, Hastelloy and Kynar probe body, sapphire and quartz windows or lens

Fiber Optics Low-hydroxy silica, multimode fibres, hundreds of meters

Update Time A few seconds to minutes

Online Analysis Yes

Warm-Up Time 60 min

Measurement Continuous

Repeatability 0.1% or less

Linearity Over the entire measurement range

Laser Safety Required

Costs ($) 60,000÷150,000 (analyzers for process applications, depending on the packaging, ruggedness, availability of analyzer standardization, and availability of simultaneous multichannel capability) 20,000 (a benchtop, low-resolution Raman instrument with probes and other accessories) 50,000÷100,000 (laboratory Raman instruments, depending on the technology (dispersive or FT-based) and also available sampling accessories) 15÷30 per foot per channel (optical fibres (consisting of three cables) for process installation, depending on the packaging options) 2,000÷15,000 (the fiber optics probe, depending on the application requirements and required ruggedness)

Advantages and Disadvantages of Mid-IR, Near-IR, and Raman Methods

NIR Absorption Mid-IR Absorption Raman Scattering

Selection rule Change in dipole moment Change in dipole moment Change in polarizability

Spectral band profile Overtone/combination bands, broad (nonspecific)

Fundamental band, narrow (high specificity) Fundamental bands, narrow (high specificity)

Sensitivity Moderate (ppm, low percentage) Very high (ppb, ppm) Low (low percentage, ppm in favourable cases)

Qualitative identification Difficult Yes. Extensive spectral library available Yes. Comprehensive library not available

Sample Transparent, bubble and particulate free liquids Powder samples require diffuse reflectance probe

Transparent liquid, thin solid pellets and ideal for gases. Special ATR probes needed

Same probe is used for all samples; liquids, slurries, emulsions, powders, solids, samples with particulates and bubbles

Signal-to-concentration relationship Logarithmic Logarithmic Linear

Quantitative analysis Mathematical/statistical modeling Simple arithmetic possible Simple arithmetic possible

Transfer of calibrations Difficult Difficult Relatively easy

Sample handling Yes Yes No, noninvasive or in situ

Water interference Good sensitivity to and interference by water Very high sensitivity to and strong interference by water

No or minimal water interference

Temperature dependence Sensitive to process temperature variation

Sensitive to process temperature Wide temperature variation tolerated

Sampling probe Double sided, single sided when used with reflectance

Double sided or special ATR probes Single ended

Probe fouling More likely More likely Less likely or not likely with noninvasive

Remote via fiber optics Long fibres, low hydroxy silica fibres Short fibres, expensive chalcogenide fibres Long fibres, low hydroxy silica fibres.

Wetted optical window Inert (sapphire, silica, quartz) Fragile (ZnSe, CaF2, KBr) Inert (sapphire, silica, quartz) Typical Process Applications for Raman Spectroscopy

Industry Process Applications

Chemical processing

Endpoint determination, Reaction monitoring, Hydrocarbon analysis, Emulsion polymerization, Copolymer reactions, Heterogeneous catalytic reactions, Nitration reactions, Esterification reactions, Batch and continuous distillations, Chemical reactor safety and efficiency, monitoring, Polymer crystallinity, Inorganic analysis

Petrochemical Monitoring xylene separation process, Para xylene purity analysis, Styrene monomer/polymer reaction, Endpoint determination, Reaction monitoring

Pharmaceutical Fermentation, Cell culture monitoring, Bromination reaction, Raw material verification and screening, Intermediate analysis

Pulp and Paper Pulp bleaching, Chlorine dioxide production

Food and Beverage

Modified starch, Hydrogenation of oils and fats, Sugars, Endpoint determination, Fermentation



Table 49: Refractometers Applications Liquids and slurries. Measures the concentrations of dissolved solids or water-soluble liquids.

Materials of Construction Stainless steel and glass are standard, with Teflon gaskets

Operating Pressure Up to 70 barg

Operating Temperature Up to 1371ºC

Recommended Flow Velocity For in-line units in excess of 1.5 m/s

Ranges Spans of industrial in-line units typically range from 1.25÷1.65 RI refractive index (RI) units or 0÷100 Brix(1.333÷1.54 ORI). Some typical span requirements for a variety of applications are 1.00÷1.30 (battery acid), 1.333÷1.360 (urine), 1.333÷1.520, 1.435÷1.520, 1.300÷1.700. Other typical ranges include: in percent salinity, 0÷10% and 0÷28%; in % Brix units, 0÷10%, 0÷20%, 0÷32%, 28÷62%, 58÷90%, and 0÷90%; in freezing point of coolants, –51÷0ºC; in window-washer-fluid concentration, 0÷100%.

Speed of Response 3÷30 sec

Drift From 0.5% per month to 1% per 24 hr

Accuracy ~0.0002 RI or 0.25% (a good industrial in-line unit, having a span of 0.08 RI) 5% of span (the least accurate units) Error is 0.1% (0.05% in highprecision refractometers) ((hand-held laboratory units in % Brix units, for a range of 0÷95%). The corresponding errors in RI units are 0.0002 and 0.0001, respectively).

Costs ($) 200÷600 (portable, hand-held, battery-operated refractometers) 800÷1,500 (specialized, digital, hand-held units for battery acid, antifreeze, and window washer applications) 2,500÷4,500 (high-precision benchtop laboratory units) 5,000÷10,000 (industrial in-line transmitters) 8,000 (in-line sensors in sizes up to 75 mm) 10,000 (in-line sensors in sizes up to 100 mm) 8,000 (probe sensors) 25,000 (beverage analysis system with ±0.02 Brix Accuracy)

RI and Brix Units Note:

The index of refraction, or refractive index (RI), is the ratio between the speed of light in vacuum and the speed of light in the substance of interest. RI therefore is unity when the light travels in vacuum at a

speed of 0.3 billion m/s. The RI of air is 1.0003, and the RI of most gases, liquids, and solids is between 1 and 2.

Some industries use their own units rather than the index of refraction. Two examples are the sugar and citrus juice industries. They prefer to use the % Brix scale, which refers to the weight-percent of sugar

concentration, corresponding to the number of grams of sugar contained in 100 g of solution. Refractive Index Table [all data based on 20C]

Acetic acid 1.3718 Cycloheptane 1.4440 Glycerol 1.4729 Nonane 1.4055 Acetone 1.3588 Cyclohexane 1.4262 Glycol 1.4318 Octane 1.3975 Acrylic acid 1.4224 Cyclohexanone 1.4503 Heptane 1.3876 Pentane 1.3575 Amyl acetate 1.4012 Cyclopentane 1.4065 Hexane 1.3749 Perchloroethylene 1.5053 Benzene 1.5011 Decane 1.41203 Hexanol 1.4135 Phenol 1.5425 Butyl acetate 1.3951 Di-ethyl benzene 1.4955 Hydrazine 1.470 Propanol(n) 1.3851 Butyl alcohol 1.3993 Di-methyl benzene 1.4972 Hydrogen chloride 1.256 Pronanol(iso) 1.3776 Butylene 1.3962 Di-ethyl ether 1.3497 Lead tetraethyl 1.5198 Styrene 1.5434 Carbon disulfide 1.6295 Ethyl acetate 1.3722 Menthol 1.458 Toluene 1.4969 Carbon tetrachloride 1.4631 Ethyl alcohol 1.3624 Methyl alcohol 1.3288 Water 1.3330 Chlorobenzene 1.5248 Ethylbenzene 1.4952 Methyl ethyl ketone 1.3807 Chloroform 1.4464 Formic acid 1.3714 Nitric acid 1.397

Types Differential Refractometer (Single-Pass Design, Two-Pass Design) Critical-Angle Refractometer Reflected Light Measurement (Fiber Optic Probe)

Conclusions When used for binary mixtures, the refractometer can be a very accurate analytical tool, but it is usually unable to detect trace impurities. Mixtures with trace components having RI values close to one of the major components may act as binary samples and can give satisfactory results. The differential refractometer is more sensitive than the critical angle refractometer, but it requires a sample-handling system and is limited to applications in which the sample is clean. The critical angle refractometer can monitor dirtier streams and can be installed in line.



Table 50: Rheometers Types Cone-and-plate Parallel-disk Coaxial-cylinder Rectangular torsion Bending and

tension/compression Extensional flow rheometer Capillary rheometer

Linear Properties Elastic storage modulus vs. frequency

Viscous loss modulus vs. frequency

– – – – –

Nonlinear Properties Viscosity vs. shear rate

First normal stress difference vs. shear rate

Second normal stress difference vs. shear rate

Extensional viscosity vs. rate of extension

– – –

Frequency Range 0.01÷200 Hertz

Pressure Atmospheric

Temperature Range –150ºC÷+600ºC

Cost ($) 30,000÷200,000

Rheometer selection Note: A rheometer by definition can be used not only to detect viscosity but also to measure the viscoelastic properties of fluids, semisolids, and solids. In selecting a rheometer design to analyze a polymeric sample, the following questions should be considered: 1. What class of deformation or flow is most relevant, shear or extension (elongation) or a combination of these two basic types, such as bending? 2. Should the sample deformation rate be constant or oscillatory? A constant rate of deformation is impossible for a viscoelastic solid. For constant deformation rate experiments, what is the necessary range of shear rates or extension rates? For oscillatory deformations, what is the necessary range of frequencies? 3. Will the rheometer control the amount of stress applied to the sample (i.e., stress-controlled rheometer) or the amount of strain applied to the sample (i.e., strain/ strain-rate-controlled rheometer). Strain/strain-ratecontrolled rheometers cannot be used to measure the true value of the yield stress for weak solids. 4. Will the sample adhere to the stainless steel fixtures of the rheometer so that the no-slip boundary condition is satisfied, or will it be necessary to clamp the sample? Are large solid particles suspended in the sample, comparable in size to the gap of the proposed rheometer fixture? If so, a fixture with a larger gap must be used. 5. Is the sample corrosive, volatile, combustible, or otherwise destructive to stainless steel rheometer fixtures? To study the gelation of network-forming materials like epoxies, disposable rheometer fixtures will probably be required. 6. What is the required temperature range for testing? Liquid nitrogen cooling may be required for subambient testing temperatures. 7. What is the sensitivity required for stress or strain measurement? What is the maximum stress value to be measured or applied to the sample?

Table 51: Streaming Current or Particle Charge Analyzer Applications Batch operations, titration, and continuous monitoring; can control the clarification of beverages, dewatering, thickening of suspensions, addition of coagulant

chemicals, and treatment demand by measuring the surface charge on particles

Materials of Construction Stainless steel, silver, and Teflon

Sample Size Required ~10 cc

Cost ($) ~10,000÷15,000

Typical applications Most applications involve either titration of the sample or prior treatment in the plant, because a single reading on untreated material provides little information. This is because SCD readings are almost independent of the concentration of suspended solids. Titration can be performed with as little sample as will submerge the active part of the instrument. There are three operational steps: treatment chemical selection, sampling and control. The streaming current detector (SCD) is only one of the methods available for characterizing concentrated colloids. Another method is based on the electroacoustic effect, which is claimed to be more efficient.

Note: SCD = Streaming Current Detector

Table 52: Sulfur-in-Oil Analyzers Method of Analysis X-ray absorption X-ray fluorescence Pulsed UV Purged spectrometer

Type of Sample Crude and fuel oils, diesel, gasoline, middle distillates, kerosene, gas oil, jet fuel, and lubricating oils

Range 0÷0.5 to 0÷5% sulfur; 0.6÷1 g/ml density Lower detection limit is 50 ppm Down to 1 ppm w/w sulfur in diesel, gasoline, kerosene, and jet fuel 40 ppm÷5%

Accuracy 0.5% of full scale or 0.005 wt% S 15 ppm at a concentration of 300 ppm Repeatability at 1 ppm is ±0.02 ppm 3% of concentration

Sensitivity 0.5% of full scale or 0.0005 g/cm3 – – –

Cost ($) 40,000÷80,000 40,000÷80,000 55,000÷65,000 ~75,000

Measurement reasons

On-line analysis of sulfur in oil products is imperative, because environmental authorities are tightening the limits on sulfur levels in petroleum products. Limitations of 300 ppm in blended gasoline and 500 ppm in diesel are not uncommon. Even with an excellent hydrotreating capability, these limits are often difficult to meet, so processing must be carefully monitored. The timely information provided by continuous on-line monitoring is necessary to consistently meet sulfur content limits, especially when blending the various product or feed streams.



Table 53: Sulfur Oxide Analyzers Methods of Detection Colorimetric Conductimetric Correlation spectrometry Coulometric Electrochemical Flame photometric Infrared Thermal conductivity Ultraviolet Chromatographic

Applications Mostly for ambient air monitoring

Mostly for ambient air monitoring

For stack gas monitoring Mostly for ambient air monitoring



For stack gas monitoring Mostly for ambient air monitoring

For stack gas monitoring –

Reference Method Pararosaniline; an EPA study (CPA 70–101) found coulometry to be equivalent to this reference method.

– – – – – – – – –

Sample Pressure Where sampling is involved, the sample pressure is usually near atmospheric.

Sample Temperature Generally limited to about 49°C

Generally limited to about 49°C

Not so limited, as they usually are not in direct contact with the sample but are protected by air cooling.







–

Sample Flow Rate Usually between 2.8 to 28 alpm

Materials of Construction Because of the reactivity of sulfur oxide gases, glass, Teflon and stainless steel are preferred; PVC should be avoided.

Speed of Response Depend on the liquid capacity of the automated wet-chemistry system

Depend on the liquid capacity of the automated wet-chemistry system

Nearly instantaneous Depend on the liquid capacity of the automated wet-chemistry system

Nearly instantaneous Nearly instantaneous Nearly instantaneous – Nearly instantaneous –

Concentration in ambient air should stay below 0.1 ppm in the short range and below 0.02 ppm in the long range; therefore, the sensor range should not exceed 0÷1 ppm. Stack monitors require 0÷1000 ppm ranges.

Ranges

0.01÷5 ppm, but with dilution systems can measure up to 5,000 ppm


0÷100 ppm up to 0÷100%, but most applications are from 500÷10,000 ppm (this type can detect down to 5 ppm)


0÷15 ppm 0.01÷5 ppm, but with dilution systems can measure up to 5,000 ppm

0÷100 ppm up to 0÷100%, but most applications are from 500÷10,000 ppm

0÷20% 0÷100 ppm up to 0÷100%, but most applications are from 500÷10,000 ppm

–

Accuracy Absolute limit on precision is 0.005 ppm

Absolute limit on precision is 0.005 ppm

Generally, 1÷3% of full scale




0.5% of full scale Absolute limit on precision is 0.005 ppm

0.5% of full scale –

Costs ($) >500 (pocket-sized personal monitors) 2,500÷5,000 (ultraviolet laboratory spectrometers) 4000÷7000 (portable ambient monitors for multiple gas detection) 10,000÷20,000 (permanently installed ambient air quality monitors configured for multiple-sample or multiple-gas monitoring) 25,000÷35,000 (stack gas monitor, depending on materials of construction, accessories, and number of components analyzed, which can include opacity) >35,000 (passive, remote-sensing correlation spectrometers)

Typical applications The predominant sulfur oxide in the atmosphere is sulphur dioxide (SO2). Some sulfur trioxide (SO3) is also formed in combustion processes, but it rapidly hydrolyzes to sulphuric acid, which is considered to be a particulate matter. Therefore, this section concentrates on the monitoring of sulphur dioxide. In the U.S., the ultimate air quality goals (secondary standards) for sulfur dioxide are 60μg/m3 (0.02 ppm) annual arithmetic average, 260μg/m3 (0.1 ppm) maximum 24-hr concentration not to be exceeded more than once a year. The oxides of sulfur are measured both in ambient air, where their concentration is usually a small fraction of one ppm, and in stacks and other industrial emissions, where their concentrations are in hundreds of ppm.

Note: alpm = actual liter per minute



Table 54: Thermal Conductivity Detectors Applications Gases or vapors; best suited for binary gas applications such as detector on chromatographs or leak detection or for hydrogen and helium analyses, because these gases have high thermal conductivity

Design Pressure Near atmospheric

Sample Temperature 2÷43ºC

Cell Materials of Construction Brass, stainless steel, Monel

Range The full span of the analyzer should correspond to a minimum of a 2% change in the thermal conductivity of the gas mixture.

Accuracy Accuracy is 1÷2% of full scale for binary samples when the thermal conductivity of each constituent is accurately known. Published thermal conductivity data can be in error by as much as 5%. Interpretation of readings on multicomponent mixtures require additional measurements and analysis.

Cost ($) 1,600 (a portable leak detector with 10−5cc/sec sensitivity) 2,500÷6,000 (industrial analyzers for binary mixtures) 6,000÷12,000 (analyzers with higher sensitivity and/or in corrosion-resistant materials)

Main components Measuring cell, regulated power supply, Wheatstone bridge, and case temperature control. Thermal Conductivity Factors/ Ranges of Gas Mixture Compositions Suitable for Measurement by Thermal Conductivity

Thermal Conductivity Factors Ranges of Gas Mixture Compositions Suitable for Measurement by Thermal Conductivity

Gases R0* R100* Gases in the Mixture Range of Concentrations of the First Gas in the Second

An Error of 1% of Full Scale Corresponds To

Acetone 0.406 0.546 Air in carbon dioxide 0–5% 0.05%

Acetylene 0.776 0.900 Air in helium 0–2.5% 0.025%

Air 1.000 1.000 Air in oxygen 0–0% 0.4%

Ammonia 0.897 1.086 Air in sulfur dioxide 0–1% 0.01%

Argon 0.709 0.725 Argon in nitrogen 0–7% 0.07%

Benzene 0.370 0.573 Carbon dioxide in air 0–7% 0.07%

Carbon dioxide 0.614 0.690 Carbon dioxide in nitrogen 0–7% 0.07%

Carbon monoxide 0.964 0.962 Carbon dioxide in oxygen 0–6.5% 0.065%

Chlorine 0.322 0.381 Helium in air 0–0.5% 0.005% (50 ppm)

Ethylene 0.735 0.919 Helium in hydrogen 0–12% 0.12%

Ethane 0.807 0.970 Hydrogen in helium 0–10% 0.1%

Helium 6.230 5.840 Hydrogen in nitrogen 0–0.3% 0.003% (30 ppm)

Hydrogen 7.130 6.990 Nitrogen in argon 0–5% 0.05%

Methane 1.318 1.450 Nitrogen in carbon dioxide 0–5% 0.05%

Nitrogen 0.996 0.996 Nitrogen in hydrogen 0–2.5% 0.025%

Oxygen 1.043 1.052 Nitrogen in oxygen 0–55% 0.55%

Pentane(n) 0.520 0.702 Oxygen in air 0–38% 0.38%

Refrigerant 12 0.354 0.356 Oxygen in carbon dioxide 0–4.5% 0.045%

Sulfur dioxide 0.344 0.377 Oxygen in nitrogen 0–52% 0.52%

Sulfur dioxide in air 0–3% 0.03% Advantages Composition measurement by detecting the thermal conductivity of gases is one of the simplest and oldest methods of analyzing process streams. This technique takes advantage of the facts that different substances have a varying

capacity to conduct heat energy from a heat source. This ability differs for each gas. It is called thermal conductivity and can be expressed in various unit systems such as BTU/hr/ft2/°F/in.; W/sec/cm2/°C/cm; kiloergs/sec/cm2/°C/cm, and so on. This is a simple, rugged, inexpensive, reliable, and easily maintained, but nonspecific, analyzer that can determine the composition of only binary mixtures. It is not very sensitive, nor is it very fast, but it is well suited for many chromatographic and leak detection applications.

Limitations Although simple in design, this analyzer has a major limitation: only binary mixtures can be accurately measured by it. The analyzer is nonspecific; because it measures the total thermal conductivity of the process sample, it cannot distinguish or identify the component that causes the conductivity change in multicomponent mixtures. Therefore, its applications are limited to binary or binary-like mixtures. Some industrial gas streams are binary mixtures and do require analysis.

Conclusions The advantages of the thermal conductivity analyzer include its low cost, simplicity, reliability, and reasonable speed of response. Its main limitation is that it can measure only binary mixtures. In addition to its nonspecific nature, the need for empirical calibration further restricts its use. It is also recommended that all water vapors be removed from the measurement sample by drying. Because of the above-listed limitations, its applications are few and usually involve binary mixtures for applications such as leakage measurement and chromatography or the detection of hydrogen or helium in applications where the thermal conductivity of the “background” gases is low and relatively constant.



Table 55: Total Carbon Analyzers Methods of Detection Nondispersive infrared (NDIR) Aqueous conductivity with ultraviolet (UV)

irradiation Coulometric detectors Colorimetry Flame-ionization detection (FID)

Samples 0.01÷40 cc (laboratory sample sizes range) 0.25÷30 cc/min (the sample flow rates range for in-line applications)

Flowing Sample Solids Content Up to 1000 mg/l; size of particles up to 200 μm in diameter

Materials of Construction Glass, quartz, Teflon, stainless steel, Hastelloy, polyethylene, PVC

Measurement Cycle Time 3÷7 min (TC requires 2.5 min and TOC requires 5 min) including sample pretreatment

Initially, 3÷7 min, then continuous with speed of response of 30 s; results can be updated every 1 s

5÷7 min including sample pretreatment 3 hr for 1÷25 samples 3÷7 min (TC requires 2.5 min and TOC requires 5 min) including sample pretreatment

Utilities or Reagents Required Air (4.6 alpm), oxygen, nitrogen (carrier gas flow is 100 cc/min at 3.5 barg), hydrogen, mineral acid (0.1 gal per month of sulfuric or phosphoric), oxidizing reagent, buffer, deionized water

Ranges 0.002÷50,000 ppmC (0÷5%) 0.05÷50,000 ppbC 3 ppmC, 100%C 0÷20, 20÷700 ppmC 0÷2 and 0÷30,000 ppmC

Sensitivity 10 ppbC or 1% of full scale, whichever is greater 1 ppbC 0.01gC 300 ppbC 0.1 or 0.5% of full scale, whichever is greater

Accuracy 1÷5% of full scale as a function of design, sample size, and range

Costs ($) 20,000÷25,000 (including PC and software) 25,000÷28,000 (with auto-sampler)

20,000÷25,000 (including PC and software) 25,000÷28,000 (with auto-sampler)

20,000÷25,000 (a manual analyzer) 34,000÷36,000 (with autosampler and software)

600÷900 (portable colorimeters) 5,600 (spectrophotometers) 535 (COD reactor) 250 (reagent kit)

–

Advantages and Limitations A TOC analysis is very rapid and accurate, but it measures only the organic carbon content and it therefore does not detect the pollutant load that is represented by nitrogen-based molecules. A BOD analysis is slow, but it measures all

molecules that exert an oxygen demand on the receiving waters, and its readings will vary if the bioassay used is changed.

Thus, the BOD, in addition to being a lengthy five- or seven day analysis, gives significantly different readings as a function of the bioassay used. The COD analysis suffers from shortcomings in oxidation efficiencies, although its analysis

time is reduced. Direct correlation between TOC, BOD, and COD usually is not possible. On the other hand, with proper interpretation, the TOC can represent a rapid and frequently accurate method of assessing the pollution load levels of

municipal and industrial wastes. Official Methods of TOC Determination

Oxidation Method Detector Analytical Range Official Methods

Combustion NDIR 0.004÷25,000 mg/l EPA 415.1, 9060A Standard Method 5310B ASTM D2579 ASTM D5173 DIN 38 409 H3 ISO 8245 AOAC 973.47 USP 643

Combustion Coulometric 2÷50,000 mg/l ASTM D4129 ASTM D513

UV NDIR or conductivity 0.0005÷0.5 mg/l USP 643 ASTM D4839 ASTM D4779

UV/persulfate Membrane/conductivity 0.0005÷50 mg/l USP 643 Standard Method 5310C ASTM 5904

UV/persulfate NDIR 0.002÷10,000 mg/l EPA 415.1, 9060A Standard Method 5310C ASTM D2579 ASTM D4839 ASTM D4779 ASTM D5173 ISO (Draft) 8245 AOAC 973.47 USP 643

Heated persulfate NDIR 0.002÷1,000 mg/l EPA 415.1, 9060A Standard Method 5310C ASTM D2579 ASTM D5173 ISO (Draft) 8245 AOAC 973.47 USP 643

Note: TC = Total Carbon TOC = Total Organic Carbon BOD = Biochemical Oxygen Demand COD = Chemical Oxygen Demand



Table 56: Toxic Gas Monitoring Types of Devices

Personnel protection and dosage sensors Continuous industrial monitors/alarms/transmitters

Dosimeter and color change badges for exposure monitoring

Direct reading dosimeter (indicating) tubes

Radon canisters

Sorption tubes for thermal desorption

Air sampling pumps

Thermal desorption instruments

Pocket-sized electrochemical monitors

Calibrators for toxic gas monitors

Electrochemical cells (membrane diffusion) or semiconductor

Infrared Ultraviolet Ionization detectors

Fluorescence and chemiluminescence

Chromatograph Mass Spectrometer

Applications Safety related monitoring of ambient air and enclosed spaces for toxic gases and vapors, reduced oxygen, and radon; also used for the monitoring of fugitive emission sources in manufacturing or processing typically from stacks, valves, and fume hoods

Costs ($) 350÷500 (a package of five badges with prepaid analysis)

2÷4 per tube 200 (hand pump) 800 (automated pump

45÷250 per point (for testing service)

35÷120 per tube

800÷2,000; ~1,200 (an average pump)

1,700÷20,000 400÷700 (single gas monitors) 800÷2,900 (multiple gas monitors)

850÷15,000 300÷1,700 per point of detection

500÷2,000 per point of detection

11,300÷34,000 1,500÷3,500 (for photoinization)

– 35,000÷60,000 (unit equipped with sample multiplexer and column program/backflush)

140,000 (typical for an instrument equipped with a 64-channel stream multiplexer)

Selected Toxic Gases and Vapors (10 ppm and below)*

Name of Element or Compound TLV-TWA, ppm STEL, ppm TLV-C, ppm Human Carcinogenity Status** Name of Element or Compound TLV-TWA, ppm STEL, ppm TLV-C, ppm Human Carcinogenity Status**

Acetic acid (vinegar) 10 – 25 – Hydrogen cyanide – – 4.7 –

Acrolein – – 0.1 A4 Hydrogen fluoride – 0.05 3 –

Acrylonitrile 2 – – A3 Hydrogen selenide 0.05 – – –

Aniline 2 – – A3 Hydrogen sulfide 10 15 – –

Arsine 0.05 – – – Methyl isocyanate 0.02 – – –

Benzene 0.5 2.5 – A1 Methyl mercaptan 0.5 – – –

Biphenyl 0.2 – – – Naphthalene 10 15 – A4

Boron trifluoride – – 1 – Nickel carbonyl 0.05 – – –

Bromine 0.1 0.2 – – Nitric acid 2 4 – –

Bromine pentafluoride 0.1 – – – Nitrobenzene 1 – – A3

Bromoform 0.5 – – A3 Nitrogen dioxide 3 5 – A4

1,3-Butadiene 2 – – A2 2-Nitropropane 10 – – A3

Carbon disulfide 10 – – – Osmium tetroxide 0.0002 0.0006 – –

Carbon tetrabromide 0.1 0.3 – – Oxygen difluoride – – 0.05 –

Carbon tetrachloride 5 10 – A2 Ozone 0.05 Heavy Work 0.1 Light Work

– – A4

Carbonyl difluoride 2 5 – – Pentaborane 0.005 0.015 – –

Chlorine 0.5 1 – A4 Phenylhydrazine 0.1 – – A3

Chlorine dioxide 0.1 0.3 – – Phosgene 0.1 – – –

Chlorine trifluoride – – 0.1 – Phosphine 0.3 1 – –

Chloroform 10 – – A3 Phosphorus oxychloride 0.1 – – –

bis-(Chloromethy)ether 0.001 – – A1 Phosphorus pentachloride 0.1 – – –

Diborane 0.1 – – – Phosphorus trichloride 0.2 0.5 – –

Dichloroacetylene – – 0.1 A3 Silane 5 – – –

Dimethyl hydrazine 0.01 – – A3 Sodium azide – – 0.11 A4

Dimethyl sulfate 0.1 – – A3 Stibine 0.1 – – –

Ethylene oxide 1 – – A2 Sulfur dioxide 2 5 – A4

Fluorine 1 2 – – Sulfur tetrafluoride – – 0.1 –

Formaldehyde – – 0.3 A2 Tellurium hexafluoride 0.02 – – –

Germane 0.2 – – – Thionly chloride – – 1 –

Hydrazine 0.01 – – A3 o,p-Toluidine 2 – – A3

Hydrogen bromide – – 3 – Vinyl bromide 0.5 – – A2

Hydrogen chloride – – 3 – Vinyl chloride 1 – – A1 Note: *Abstracted from 2001–2002 Threshold Limit Values American Conference of Governmental Industrial Hygienists, 2001. **Carcinogenicity: A1-Confirmed Human Carcinogen; A2-Suspected Human Carcinogen; A3-Confirmed Animal Carcinogen with Unknown Relevance to Humans; A4-Not Classifiable as a Human Carcinogen. TLV-TWA = Threshold Limit Values-Time-Weighted Averages STEL = Short-Term Exposure Limit TLV-C = Threshold Limit Values -Ceiling



Table 57: Turbidity, Sludge, and Suspended Solids Laboratory unit Industrial unit Types

Manual Flow-through Probe Flow-through

Design Pressures Up to 17 barg

Design Temperatures 120°C standard; 232°C special

Construction Materials Stainless steel, glass, plastics

Ranges In ppm silica units, from 0÷0.5 to 0÷1000 Backscattering designs available from 10÷5000 ppm up to 5÷15% Ranges in JTU units from 0÷0.1 to 0÷10,000 In NTU units, from 0÷1 to 0÷200 In FTU units, from 0÷3 to 0÷1000 Sludge density probe with reciprocating piston has a range from 0÷0.1 to 0÷10% of suspended solids

Accuracy 0.5÷2% of full scale for most designs, 5% of full scale for the reciprocating piston probe type suspended solids sensor, which is used on sludge applications

Costs ($) 100 per bottle (standard reference solutions for calibration) 750÷2,000 (laboratory turbidity meters) 2,000 (laboratory nephelometers with continuous-flow attachment) 2,500÷5,000 (industrial turbidity transmitters, depending on features and materials of construction) 7,500 (sludge-density-detecting, self-cleaning probe with internal reciprocating piston and indicating transmitter) 5,000÷6,000 (ultrasonic suspended solids transmitters)

Turbidity Analyzer Design Forward-Scattering or Transmission Type (Dual-Beam Design, Laser-Type Meter, Suspended Solids and Sludge Density Sensors Scattered Light Detectors (Nephelometers) Backscatter Turbidity Sensors

Conversion Between Different Units of Turbidity

Turbidity Unit Kieselgur Units (SiO2)

Absolute Units A.E.

Formazin Turbidity Units E.B.C.

Formazin Turbidity Units A.S.B.C.

Formazin Turbidity Units A.S.B.C.

Helm Units (BaSO4)

Mastic Units Langrohr Units Reciprocal

Kieselgur units according to German Standards method (1 mg SiO2 per liter dist. H2O = 1 ppm)

1 0.000445 0.1 6.9 1 4 8 0.000465

Absolute units A.E. (Zeiss–Pulfrich turbidity unit)

2250 1 – – – – – –

Formazin turbidity units E.B.C. 10 0.00445 1 69 10 40 80 0.00465

Formazin turbidity units A.S.B.C. 0.145 0.000065 0.0145 1 0.145 0.58 1.16 0.0000675

Jackson turbidity units 1 0.000445 – – – – – –

Helm units (BaSO4– Suspension) 0.25 0.00011 0.025 1.72 0.25 1 2 0.000116

Mastic units (1 drop mastic solution per 50 ml dist. H2O; 50 drops ~1 ml)

0.125 0.000056 0.0125 0.86 0.125 0.5 1 0.0000582

Langrohr units according to German Standards method, reciprocal (cm light path at 25 mm dia.)

2150 0.956 – – – – – –

Conclusions Turbidity meters (similarly to the nephelometers) measure the cloudiness of a fluid by detecting the intensity of transmitted or reflected light. The cloudiness detected by turbidity meters is caused by finely dispersed suspended particles

that, when exposed to a visible or infrared (IR) light, will scatter it. The cloudier the process fluid (the higher its turbidity), the more scattering will occur and therefore the less light will be transmitted through a sample. If the sensor photocell is placed at a 90° angle to the light path, the cloudier the process fluid, the more scattered light it will detect. Turbidity measurement is fairly simple in theory. The practical problems with these instruments include the problems posed by light source intensity changes, deposits on optical windows, and the presence of dissolved colors in the sample. Units are now available that automatically correct not only for these effects but also for the variations in the ambient light intensity and even for gas bubbles. Self-cleaning probe designs are also available. The turbidity detector should be selected on the basis of the type of information needed (transmission, 90 or 180° scatter), the nature and concentration of the solids that are to be detected, and the materials of construction required for the application.

Note: JTU = Jackson Turbidity Unit NTU = Nephelometric Turbidity Unit FTU = Formazin Turbidity Unit



Table 58: Ultraviolet and Visible Analyzers Photometers Spectrophotometers Configurations

Nondispersive analyzers in which the source radiates over its full ultraviolet (UV) spectrum, and discrete wavelengths are separated by narrow (2÷10 nm) bandpass filters. Most process analyzers are nondispersive.

Dispersive analyzers in which a prism is used to separate the spectral components of the UV spectrum. Most laboratory analyzers are dispersive.

Types of Designs Optics can be configured as single-beam, split-beam, dual-beam, or flicker photometers. The process stream can pass through a measurement chamber, or probe-type analyzers can be inserted into the process stream using a retroreflector configuration. Most detectors are capable of measuring the intensity of one wavelength at a time, whereas photodiode arrays can detect all wavelengths simultaneously.

Visible and NIR Photometers UV Analyzer Designs

Visible Photometers NIR Photometers

Single-Beam Analyzer Split-Beam Analyzer Dual-Beam, Single-Detector Analyzer Dual-Beam, Dual-Detector Analyzer Flicker Photometer Photodiode Array Spectrophotometers Scanning Spectrophotometers Retroreflector Probes

Colorimeters Split-beam design Rotating fixed filter designs

Transmission reflectance sampling Diffuse reflectance sampling

Type of Sample Gas, vapor, and liquid

Design Pressure Normally atmospheric but it can also be pressurized up to 10.7 barg to enhance sensitivity when analyzing gas samples. The fiber-optic, diode-array type of in-line analyzer can operate at up to 50 barg.

Sample Temperature Standard units operate from 0÷150ºC; stack gas analyzer can operate at up to 427ºC.

Materials of Construction Quartz and sapphire windows; other parts available in stainless steel, Hastelloy,Monel, titanium, Teflon, Kynar, and all other conventional materials

Wavelength Ranges Standard ranges include 200÷800 nm or 400÷1100 nm

Cell Lengths Standard units are from 1÷1000 mm); for fiber-optic diode-array analyzer, 0.3÷10 mm.

Repeatability ±1% of full scale

Accuracy ±2% of full scale for most; ±1% of full scale for the fiber-optic diode-array type of UV-visible analyzer

Cost ($) 2,000÷5,000 (portable battery-operated or benchtop laboratory UV-visible (200÷1000 nm) photometers, spectrophotometers, and scanning spectrophotometer) 5,000÷7,000 (portable UV stack gas monitors) 25,000÷35,000 (permanently installed stack monitoring packages, depending on materials of construction, accessories, and number of components analyzed) 20,000÷25,000 (industrial UV photometers without sampling systems) 50,000÷70,000 (photodiode array spectrophotometers) 40,000÷60,000 (fiberoptic spectrophotometers)

The Radiation Spectrum

Radiation Spectrum Wavelengths

UV 200÷400 nm

Visible 400÷800nm

IR (NIR) 0.8÷2.50μm

Typical applications UV photometers Visible photometers NIR

Residual chlorine in water in pulp and paper process Yellow color of diesel oil—ASTM units, APHA units Water in ethylene dichloride in vinyl chloride processes

Total aromatics in wastewater Food color—APHA units Water in dimethylacetamide in nylon processes

Chlorine in dichloroethane in vinyl chloride processes Color of purified organics—APHA units Alcohol in hydrocarbons in the petrochemical industry

Hydrogen sulfide and sulfur dioxide in the Claus sulfur recovery process in the petroleum refining industry

Process water in paper-making Moisture in paper slurries to check dryer efficiency

Sulfur dioxide in incinerator stack emissions Moisture in grain in the food industry



Table 59a: Laboratory Viscometers Fluids Type of Design

Pro

vid

es C

on

tin

uo

us

Sig

nal

In-l

ine D

evic

e

Lab

ora

tory

Devic

e

Tem

p. C

om

pen

sati

on

Gas

New

ton

ian

No

n-N

ew

ton

ian

(pse

ud

op

last

ic,

dil

atan

t, p

last

ic

soli

d, th

ixotr

op

ic,

and

rh

eop

ecti

c

typ

es.)

Maxim

um

Desig

n

Pre

ssu

re,

PS

IG.

(1 B

ar

= 1

4.2

PS

I)

Maxim

um

Desig

n

Tem

pera

ture

°F

(°C

= [

°F −

32]/

1.8

)

Inaccu

arc

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±%

) (1

) B

ased

on

Fu

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(2

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ased

on

M

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($)

Bubble time Manual – – √ – – √ – ATM. 77 2÷10(2) 13 CC Glass 100÷250

Manual timing – – √ – – √ – ATM. 300 0.35(2) 20 CC Glass 75÷300 (capillary tubes) 500÷3,000 (thermostatic baths)

Capillary tube

Auto timing – √ √ – – √ – ATM. 300 0.01(2) 20 CC Glass 5,000÷8,000

Influx – – √ – – √ √ 100 300 2.0(2) 0.7 CC Hardened stainless steel 1,500÷3,000 Capillary extrusion Efflux – – √ – – √ √ 5,000 640 2.0(2) 30 CC Hardened stainless steel 5000÷15,000

70,000 (computerized processability tester)

Saybolt – – √ – – √ – ATM. 250 0.1(2) 60 CC

Ford cup – √ √ – – √ – ATM. 80 2.0(2) 150 CC

Zahn cup – – √ – – √ – ATM. 80 2.0(2) 44 CC

50÷300 (cup) 250 (calibration) 500÷1,500 (thermostatic bath

Efflux cup

Auto timing – – √ – – √ √ ATM. 80 5.0(2) –

Aluminum, brass, stainless steel

2,000 and up

Manual – – √ – √ √ – ATM. 300 0.1÷1(2) 30 CC 200÷1,000 Falling ball

Automatic – √ √ – – √ √ 15,000 350 0.1÷1(2) 70 CC

Glass and corrosion-resistant alloys 21,000 (research unit used in petroleum industry)

Manual – – √ – – √ √ ATM. 400 0.5÷1(2) 2÷10 CC 100÷250 (hand tubes) up to 4,000 (units operated with stopwatch) 10,000 (automatically operated viscometer with computer interface)

Falling needle

Automatic – – √ √ – √ √ ATM. 400 0.5÷1(2) 2÷10 CC

Wetted parts are quartz, borosilicate; needles are glass

–

Coaxial-cylinder

– – √ – – √ √ ATM÷ 20,000

80÷500

1.0(2) ÷2.0(1) 1÷500 CC 1,750 (benchtop or battery-operated units (1÷2% of full scale) 2,000÷10,000 (more automated and more accurate units) 17,000 (tapered bearing simulator viscometer) 25,000 (digital, computer-compatible, torque transducer with multiple displays) 25,000÷35,000 (R&D high-shear viscometers) 40,000 (high-pressure testing stations with digital temperature control)

Rotational

Cone and plate – – √ – – √ √ ATM. 750 0.5(2) 0.1 CC

Stainless steel, nickel-plated brass, plastic, ceramic, platinum

3,000÷5,000 (laboratory units with temperature controls) 7,000 (portable, self-calibrating units) 35,000 (Mooney viscometer per ASTM and ISO) 85,000 (rubber process analyzer)

Piston Travel time √ √ √ √ – √ √ 10,000 600 2(2) In-line Stainless steel and Teflon 7,000 (sensor with explosion-proof transmitter) >4,500 (standard units)



Table 59b: Industrial Viscometers Fluids

Type of Design

Pro

vid

es C

on

tin

uo

us

Sig

nal

In-l

ine D

evic

e

Lab

ora

tory

Devic

e

Tem

p. C

om

pen

sati

on

Gas

New

ton

ian

No

n-N

ew

ton

ian

(pse

ud

op

last

ic,

dil

atan

t, p

last

ic

soli

d, th

ixotr

op

ic,

and

rh

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ecti

c

typ

es.)

Maxim

um

Desig

n

Pre

ssu

re,

PS

IG.

(1 B

ar

= 1

4.2

PS

I)

Maxim

um

Desig

n

Tem

pera

ture

°F

(°C

= [

°F −

32]/

1.8

)

Inaccu

arc

y (

±%

) (1

) B

ased

on

Fu

ll S

cale

(2

) B

ased

on

M

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($)

Differential pressure

√ √ √ – – √ – 670 900 1÷2(1) 1÷4 GPH 3,000÷4,000 (balanced dual-capillary element without d/p transmitter for fuel oil service) Continuous capillary

Back pressure √ √ √ – – √ – 500 210 1.0(1) 1 GPH

Hardened stainless steel or other corrosion-resistant metals –

Ball or slug – √ √ √ – √ √ 300 350 1.0(1) – 7,000÷16,000 (falling ball viscometer) 23,000 (high-pressure design with digital readout of ball roll time corrected for density)

Piston – √ √ √ – √ √ 500 650 1.0(1) – 2,500÷8,000 (a driven-piston element)

Falling element

Needle – √ √ √ – √ √ 2,000 662 1.0(1) –

Hardened stainless steel or other corrosion-resistant metals

–

Single float √ √ √ – – √ √ 650 450 4.0(2) 0.75÷2 GPM

Two-float √ √ √ – – √ – 300 450 2÷4(2) 0.25÷2.5 GPM

1,500÷3,000 (two-float indicators with brass or stainless steel fittings in sizes from 12 to 38 mm)

Float

Concentric √ √ √ √ – √ √ 650 450 2÷4(2) 2 GPM

Same choices as for variable-area flow meters

8,000 (38-mm transmitter in stainless steel with 300 PSIG flanges)

Blade – √ √ – – √ √ 375 150 1.0(1) Up to 2 m/s Wetted parts, stainless steel; sealing ring, silicone rubber

–

Piston √ √ √ √ – √ √ 10,000 600 2.0(2) – Stainless steel and Teflon 6,000÷8,000 (sensor with explosion-proof transmitter)

Oscillating

Torsional √ √ √ √ – √ √ 5,000 850 2.0(2) – Hardened stainless steel 15,000 (microprocessor-based temperature-compensated transmitter)

Cone and plate √ √ √ – – – √ 100 400 0.5(1) 25 CC

Kneader √ √ √ – – – √ ATM. 570 1.0(1) 80 CC

Plastometer

Capillary – – √ – – – √ 5,000 570 2.0(1) 0.6 #/HR

Hardened stainless steel 10,000÷60,000 (depending on features and on degree of automation)

Cone disc sphere

√ √ √ √ – √ √ 1,000 650 1.0(1) – 15,000÷25,000 (variable-speed microprocessor-based units)

Agitator power √ √ – – – √ √ 125 200 ~5.0(1) – –

Rotational

Double cylinder

√ √ – – – √ √ 145 300 1.0(1) –

Hardened stainless steel

–

Reed √ √ √ √ – √ √ 3,000 300 1.0(1) – Vibrational

Rod √ √ √ √ – √ √ 1,485 500 1.0(1) –

Wide selection of corrosion-resistant materials and coatings

3,000÷5,000 (depending materials of construction and transmitter features)

Coriolis Torsional √ √ – √ – √ √ 1,440 302 5.0(2) or ± 0.5 cP

– Wide selection of corrosion-resistant materials and coatings

400÷20,000 (depending on line size for the in-line treatment)



Table 60: Water Quality Monitoring Measured Water Quality Parameters Ammonia Color Mercury ORP Temperature Total oxygen demand (TOD)

Biochemical oxygen demand (BOD) Conductivity Nitrates Ozone Total carbon (TC) Turbidity

Chemical oxygen demand (COD) Dissolved oxygen (DO) Odor, pH Total inorganic carbon (TIC) Volatile organic compounds (VOC)

Chlorine Fluoride Oil Phosphorus Total organic carbon (TOC) Physical Variables Air temperature, rainfall, river flow or stage (level), sunlight, wind direction and speed

Cost ($) Costs vary widely, depending on system requirements and components to be measured. For example, a single-parameter measuring system could cost as little as $3000, whereas a completely integrated monitoring system capable of simultaneous measurement of multiple volatile organic components at the ppb level and equipped with a full complement of user-specified data transmission options may cost as much as $75,000. Sample system, installation, and the cost of building a suitable shelter can double the total cost.

Categories of Monitors Monitoring for General Use Regulatory Compliance Monitoring Industrial Monitoring

Monitoring System Components Sampling Systems Sensors and Analyzers Data transmission/ logging section

Duckbill Samplers

Sample Transport

Ion-Selective Electrodes (Conductivity, pH, Oxidation-Reduction Potential) Oxygen Demand Detectors Dissolved Oxygen Sensors Total Organic Carbon and Total Carbon Analyzers Turbidity Meters Nephelometers Wet Chemistry and Autotitration Analyzers Volatile Organic Compounds Monitors

Water Quality Parameters Partial List of Measured Components in Water

Components Typical Instrument Measuring Range

Analysis Method Components Typical Instrument Measuring Range

Analysis Method

Acidity 1.0÷3.0 pH Titration Hardness (CaMg) 0÷2.5 ppm Titration

Alkalinity 0÷300 ppm Titration Hydrazine 0÷50 ppb Colorimetry

Aluminum 0÷50 ppb Colorimetry Hydrogen sulfide/sulfide 0÷500 ppb Colorimetry/ISE, chromatography

Ammonia 0÷10 ppm Colorimetry, ISE, chromatography

Iron 0÷20 ppb Colorimetry

Boron fluoride 0÷500 ppm ISE Lead 0÷1 ppm ISE, chromatog

Bromide 0÷2.0 ppm ISE Manganese 0÷200 pm Colorimetry

Cadmium 0÷20 ppm ISE, chromatography Nitrate/nitrite 0÷1 ppm Colorimetry

Calcium 0÷300 ppm Titration, ISE Phenols 0÷5 ppm Colorimetry

Chloride 0.1÷200 ppm ISE, colorimetry Phosphate 0÷1 ppm Colorimetry

Chromate 0÷100 ppb Colorimetry Silica 0÷10 pp Colorimetry

Copper 0÷20 ppb Colorimetry, ISE, chromatography

Sodium 0÷10 ppb ISE

Cyanide 0÷100 ppb Colorimetry, titration, ISE, chromatography

Urea 0÷100 ppm Colorimetry

Fluoride 0÷2.0 ppm ISE Note: ISE = Ion-selective electrode



Table 61: Wet Chemistry and Autotitrator Analyzers Types of Designs Autotitrator, volumetric devices operated to pH or color change end points Colorimetric wet-chemistry analyzers Flow injection analyzers (FIA)

Samples No suspended solids are allowed when colorimetric units are used, and minimal solids are allowed with the others.

Accuracy 1÷3% full scale; accuracy a function of the calibration

Costs ($) 10,000÷100,000 (on-line industrial units depending on what the unit does) >15,000 (automatic laboratory units for automatic preparation of up to 36 sample tubes, with operations including the dispensing of diluents and titrants into each, stirring, measuring, and recording their pH values, and then automatically moving sample tubes to the rinsing station)

Type of Reaction 1. Acid-base 2. Oxidation-reduction (ORP) 3. Complexation 4. Precipitation

– –

Method of End-Point Determination 1. Colorimetric (using pH-sensitive dyes) 2. Electrochemical electrodes (voltage (potentiometric, such as pH, specific ions, etc.), current (amperometric), resistance (conductivity), or total charge (coulometric)) 3. Spectrophotometric or photometric (which use the changes in radiation absorption to detect the end point (a form of the colormetric detector but no added reagent is required))

– –

Process Control 1. Continuous type 2. Batch type

– –

Analyzer Types High-Precision Volumetric Analyzer Simple Volumetric Analyzer

1. High-Precision Colorimetric Analyzers (Segmented Flow Analyzer, Split-Beam Colorimeter) 2. Simple Colorimetric Analyzers 3. On/Off Batch Colorimeters

Laboratory FIA Industrial FIA

ro ep in ten 001 01 e_measuring parameters data collection and transmission

Documents

data transmission

regulation omv petrom

si base units

si derived units

omv petroms

si prefixes

minimal measuring requirements

measurement devices