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SF Measurement Guide: Working Group
SF Measurement Guide: Working Group
WORKING GROUP
B3.40
APRIL 2018
SF6 MEASUREMENT GUIDE
WG B3.40
Members
E. DUGGAN, Convenor IE B. HARDY, Secretary US
J. POTTER UK M. PRUEFERT DE
I. RING IE S. STANGHERLIN CH
T. SCHWARZE DE D. MUTTER CH
R. KURTE DE N. MAHDIZADEH CH
A. MINOTTI CH M. INVERSIN FR
L. KORPINEN FI Z. XIAOXING CN
F. MEYER CH M.C. LESSARD CA
P. PILZECKER DE
Copyright © 2018
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EXECUTIVE SUMMARY
While undertaking work to develop a previous brochure, SF6 Analysis for AIS, GIS and MTS
Condition Assessment [25] it was noted that there are inconsistencies in the manner in which SF6 gas
measurements are undertaken and also in how the results are reported. It was felt that these issues were
of sufficient importance to justify a dedicated brochure specifically to address them.
This brochure is the result of this additional work and it sets out to promote the use of consistent units
of measurement for SF6 content, humidity and decomposition products. It examines the practice of SF6
measurements and outlines the precautions necessary to ensure that valid results are obtained.
It also takes the opportunity to revisit the historic frost/dew point limit of −5 °C for SF6 humidity and
explores the use of this limit in different ambient conditions. Certain circumstances are identified when
this limit may not be the most appropriate value and that an alternative approach may be more
beneficial. Related to this humidity limit is the phenomenon of the transfer of humidity between the
gas and moisture on the internal surfaces of the enclosure and in the polymeric materials within the
enclosure. This absorption/desorption phenomenon is both time and temperature dependent and
presents problems in interpreting humidity measurements carried out under different equipment
temperatures or over time. Manufacturers and users of SF6 insulated equipment have adopted different
approaches to accommodating this temperature dependency and these different approaches are
discussed. The pressure dependency of frost/dew point is also explained but shown to be immaterial in
the context of this absorption/desorption effect.
The initial sections of this brochure address definitions, preferred units and standards. There is then a
detailed discussion of the calibration of test equipment. This section seeks to raise awareness of the
role that standards laboratories and, in particular, the use of references or carrier gases in the calibration
process. We highlight the fact that the calibration performed on an instrument using one reference gas
may not be applicable when used with other gases.
The section on measurement techniques is very detailed as would be expected. As well as providing a
step-by-step guide to the measurement process, it includes discussions on some unique, but limited,
situations that can occur in practice.
And finally, the last section summarizes the findings of the Working Group.
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CONTENTS
1. INTRODUCTION................................................................................................................. 11
2. DEFINITIONS....................................................................................................................... 13
3. UNITS ................................................................................................................................... 19
3.1. SI UNITS ....................................................................................................................................................................... 19
3.2. PREFERRED UNITS ....................................................................................................................................................... 19
3.2.1. Temperature ................................................................................................................................................... 19
3.2.2. Density ............................................................................................................................................................. 20
3.2.3. Pressure ........................................................................................................................................................... 20
3.2.4. Concentration of Insulation Gases .............................................................................................................. 21
3.2.5. Decomposition Products ................................................................................................................................ 21
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6. HUMIDITY ............................................................................................................................ 31
6.1. IDEAL GAS LAW AND VAPOUR PRESSURE CURVE ............................................................................................. 31
6.2. EQUATIONS, CONVERSIONS, UNITS AND VAPOUR PRESSURE ...................................................................... 31
6.3. DEW POINT VS. FROST POINT ............................................................................................................................... 31
6.4. SF6 PRESSURE AND TEMPERATURE SPECIFICATIONS IN IEC STANDARDS...................................................... 32
6.5. TEMPERATURE DEPENDENCE OF FROST/DEW POINT ....................................................................................... 32
6.6. ABSORPTION, ADSORPTION AND DESORPTION WITHIN SF6 INSULATED EQUIPMENT ............................ 32
6.7. DIELECTRIC WITHSTAND OF SF6 VERSUS HUMIDITY .......................................................................................... 34
6.8. RECOMMENDED HUMIDITY UNITS ......................................................................................................................... 34
6.8.1. Water content of SF6 cylinders ................................................................................................................... 34
6.8.2. Water content of SF6 in non-switching gas compartments ..................................................................... 34
6.8.3. Water content of SF6 in switching gas compartments ............................................................................. 35
6.9. DEW POINT LIMIT SF6 GAS COMPARTMENTS .................................................................................................... 35
6.9.1. −5 °C Frost Point Threshold ......................................................................................................................... 35
6.9.2. Normalisation of the Frost Point Value to 20°C ....................................................................................... 35
6.9.3. Limitations of ‘−5 °C frost point Concept at Low Temperatures ........................................................... 35
6.9.4. New concepts for recommended humidity limits ...................................................................................... 36
6.9.5. Conclusion ....................................................................................................................................................... 37
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9. CONCLUSIONS.................................................................................................................. 57
10. REFERENCES........................................................................................................................ 59
APPENDICES .................................................................................................................................... 61
A. IDEAL GAS AND SF6 VAPOUR PRESSURE CURVE....................................................... 62
A.1. Ideal Gas Law ............................................................................................................................................... 62
A.2. Temperature Induced Pressure Change in a Closed Vessel ................................................................... 62
A.3. Temperature and Pressure induced Frost/Dew Point Change in a Closed Vessel ............................. 62
A.4. SF6 vapour pressure curve ........................................................................................................................... 64
A.4.1. SF6 Triple Point............................................................................................................................................... 65
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LIST OF TABLES
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LIST OF FIGURES
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1. INTRODUCTION
The use of SF6 as an insulating and arc extinguishing medium is vital to the operation of high voltage
electrical equipment and hence the delivery of electrical energy. While efforts are being made to find
an alternative to SF6, one which will have a much lower global warming potential, SF6 will continue
to be critically important for many decades to come. Notwithstanding these efforts, it is incumbent on
all involved in the management of SF6 gas, to take all possible measures to minimize the releases of
SF6 to atmosphere.
CIGRÉ is instrumental in leading these efforts and has produced several technical brochures to assist
in the gas management process. These brochures have covered issues such as SF6 handling and re-
cycling, design recommendations to eliminate the leakage of gas from electrical equipment, methods
to reduce the use of SF6 during type and routine testing of equipment, and SF6 gas analysis as a non-
invasive means to determine the condition of in-service equipment and thus reduce the need to open
gas compartments.
The latest brochure further develops concepts that were reported in a previous technical brochure, SF6
Analysis for AIS, GIS and MTS Condition Assessment [25]. While doing the work for the earlier
brochure it was noted that there were inconsistencies in the manner in which SF6 gas measurements
are undertaken and also in how the results are reported. It was felt that these issues were of sufficient
importance to justify a dedicated brochure specifically to address them.
The earlier work also involved some lengthy discussion with equipment manufacturers and users on
the appropriate humidity limits, and the phenomenon of transfer of humidity between the gas and the
internal surfaces of the enclosure and the polymeric materials within the enclosure. From these
discussion, it was evident that an explanation and analysis of these issues would be of significant
benefit to users and manufacturers alike.
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2. DEFINITION
Table 2-1 gives the general definitions of terms used within the document, some of which are from
IEC 60050 International Electrotechnical Vocabulary [1], International Vocabulary of Metrology
(VIM) [2], Guide to the Expression of Uncertainty in Measurement (GUM) [3], and BIPM Bureau
International des Poids et Mesures [4] .
Table 2-1: Definitions
Absolute error Algebraic difference between the indicated value and a comparison value
NOTE: This term is used in the “true value” approach.
Absorbed Water molecules that permeate into materials. The degree to which water
moisture permeates is dependent on the structure and type of the material.
Adsorbed Water molecules that adhere to and accumulate on the surfaces of solids.
moisture
Adjustment (of a Set of operations carried out on an instrument in order that it provides given
measuring indications corresponding to given values of the measurand.
instrument)
NOTE: When the instrument is made to give a null indication corresponding to
a null value of the measurand, the set of operations is called zero adjustment.
Calibration Set of operations that establish, under specified conditions, the relationship
between values of quantities indicated by a measuring instrument or measuring
system, or values represented by a material measure or a reference material, and
the corresponding values realized by standards
Celsius Quantity-value scale for Celsius temperature, defined by the triple point of
temperature scale water as 0.01 °C and Celsius temperature difference 1 °C = 1 K
The triple point of water is at 273.16 K. The boiling point of water, under
normal conditions, is close to 100 °C.
Contaminants Foreign substances in SF6 gas originating from the assembly, gas handling and
operation of the electrical equipment.
Decomposition Contaminants that are produced because of chemical reactions within the
Products compartment.
Some entities distinguish between contaminants produced from the dissociation
of SF6 and those produced from further reactions between these SF6 fragments
and other gases or solids within the compartment. They are referred to as
decomposition products and decomposition by-products respectively.
However, for simplicity the single term “decomposition products” is used
exclusively in this document.
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Dew point The temperature to which a gas must be cooled to start condensing water vapour
(temperature) in liquid form. Dew point is pressure dependent and must be stated with its
associated pressure. While not technically correct, it has been common practice
to use dew point below 0 °C although frost point is the correct term. Dew point
can exist below 0 °C in the form of liquid super-cooled water and is different in
value from the equivalent frost point temperature. For the same vapour pressure,
the super-cooled dew point is approximately 10 % of reading below the
corresponding frost point value (when expressed in °C). For example, a vapour
pressure of 38 Pa corresponds to a dew point of −33 °C and a frost point of
−30 °C.
Frost point The temperature to which a gas must be cooled to start deposition of water
(temperature) vapour in the form of ice. Frost point is pressure dependent and must be stated
with its associated pressure. Frost point exists only below 0 °C.
Humidity Water in the gas phase (water vapour), within a gas mixture. In general, it is the
level of humidity that is of concern, which is expressed in terms of volume ratio
(µl/l) or weight ratio (mg/kg).
Measuring range Range of values defined by the two extreme values within which a variable
(quantity) can be measured within the specified accuracy.
Moisture Water molecules attached on the surface or within the structure of solids.
Molecular weight The mass of one mole of a specific substance. It is expressed in g/mol.
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Pressure At a point of a surface, the limit of the quotient of the magnitude of the
component normal to the surface of the force acting at this point, by the area of
an infinitesimal surface containing the point, when all the dimensions of that
surface tend to zero.
NOTE 1: The surface may be the outside surface of a body or a plane surface
of a given orientation inside the body.
NOTE 2: Within most fluids, the pressure does not depend on the surface
orientation.
Relative humidity The ratio between the water vapour partial pressure and the saturation vapour
pressure at a given temperature, expressed as a percentage
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Sensitivity (of a Quotient of the change in the indication to the corresponding change in the value
measuring of the measurand.
instrument)
NOTE: For instruments with a non-linear calibration curve, the sensitivity at
any given point is a function of the value of the measurand.
Saturation vapour The maximum water vapour partial pressure that can exist at a given
pressure with temperature with respect to ice. Any attempt to increase the water vapour partial
respect to ice pressure beyond the saturation vapour pressure results in deposition
(condensation in solid form) of ice. Saturation vapour pressure is generally
expressed in Pascal (Pa).
Saturation vapour The maximum water vapour partial pressure that can exist at a given
pressure with temperature with respect to liquid water. Any attempt to increase the water
respect to water vapour partial pressure beyond the saturation vapour pressure results in
condensation of liquid water. Saturation vapour pressure is generally expressed
in Pascal (Pa).
Triple Point The point in a one-component system at which the temperature and pressure of
three phases (solid, liquid, vapour) are in equilibrium [31].
Uncertainty (of Parameter, associated with the result of a measurement, that characterizes the
measurement) dispersion of the values that could reasonably be attributed to the measurand.
NOTE 1: This term is used in the “uncertainty” approach.
NOTE 2: The parameter can be, for example, a standard deviation (or a given
multiple of it), or a halfwidth of an interval having a stated level of confidence.
Various ways of obtaining uncertainty are defined in the GUM.
NOTE.3: Uncertainty of measurement comprises, in general, many
components. Some of these components can be evaluated form the statistical
distribution of the results of a series of measurements and can be characterized
by experimental standard deviations. The other components, which can also be
characterized by standard deviations, are evaluated from the assumed
probability distributions based on experience or other information.
User adjustment Adjustment, employing only the means at the disposal of the user, specified by
(of a measuring the manufacturer.
instrument)
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Volume fraction The fraction of the volume of the constituent of interest to the total volume of
the gas, generally expressed in parts per million by volume, ppmv or its
numerically equivalent and preferred unit μl/l. Once determined, this expression
of humidity as either ppmv or μl/l has no further pressure dependence. It is also
independent of the gas type or mixture.
Volume ratio The ratio of the volume of the constituent of interest to the remaining volume
of the gas, generally expressed in parts per million by volume, ppmv, or its
numerically equivalent and preferred unit μl/l. Once determined, this expression
in either ppmv or μl/l has no further pressure dependence. It is also independent
of the gas type or mixture.
Water vapour The pressure that water vapour contributes to the total gas pressure, or the
partial pressure partial pressure exerted by the water vapour alone, generally expressed in Pascal
(Pa)
Mass fraction The fraction of the mass of constituent of interest to the total mass of the gas,
generally expressed in parts per million by weight, ppmw or its numerically
(weight)
equivalent and preferred unit mg/kg. Once determined, this expression in either
ppmw or mg/kg has no further pressure dependence, but depends on the gas type
and mixture through the molecular weight of the constituents.
Mixing ratio The ratio of the mass of the constituent of interest to the remaining mass of the
(mass ratio) gas, generally expressed in parts per million by weight, ppmw or its numerically
equivalent and preferred unit mg/kg. Once determined, this expression in either
ppmw or mg/kg has no further pressure dependence, but depends on the gas type
and mixture through the molecular weight of the constituents.
NOTE: It is a dimensionless ratio although often expressed in units of mass per
mass.
Working standard Measurement standard that is used routinely to calibrate or verify measuring
instruments or measuring systems.
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3. UNITS
3.1. SI UNITS
All units within this document are presented with a preference and correlation to International System
of Units (SI) units [5] when necessary. The preferred and/or recommended units will also be identified
with conversions supplied to easily equate historical/alternate units to the preferred units of
measurement. Where possible, these preferred units will be used throughout this document.
Temperature °C
Temperature difference K
Pressure kPa
Density kg/m3
Concentration of insulation gas % vol
Content µl/l
While those listed above are a common, consistent set of units recommended for reporting of
measurement parameters of SF6, it is recognized that a variety of alternate units have been and continue
to be used for historical reasons or as a matter of personal or company preference. Conversion factors
are provided to allow easy transformation to/from these alternate units to the preferred units of
measurement. Some example calculations are also given for clarity.
Temperature, pressure, density, decomposition products, and concentration are discussed within this
section. Humidity conversion, however, is a subject with significant complexity and warrants separate
attention and it is therefore under a separate heading.
3.2.1. Temperature
It is recommended that temperature data be reported in °C. In addition, temperature differences, or
delta temperatures, should also be reported in K. Table 3-2 lists conversions to/from alternate
temperature units.
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Example: A switchgear experiences a temperature rise, t, of 14 K. What is the equivalent temperature
rise expressed in °F?
t = 14 K
use t[°F] = t[K] · 1.8
= 14 · 1.8
t = 25.2 °F
3.2.2. Density
It is recommended that density data be reported in kg/m3. Table 3-3 lists conversions to/from some
alternate density units.
Table 3-3 Density Preferred Units and Conversion Factors
3.2.3. Pressure
It is recommended that pressure data be reported in kPa. In addition, the pressure units should be further
declared as either absolute or relative. Various pressure units are used in the field of SF6 due to
geographical and historical reasons. Some pressure measurements are referenced to relative (gauge)
pressure. Therefore, pressure data should be reported as either kPa absolute or kPa relative. Table 3-4
lists conversions to/from historically common pressure units.
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Example: Convert a gauge pressure indication of 4.5 bar to the absolute pressure in the preferred units
of kPa.
P = 4.5 barg
use P[kPa] = P[bar relative] · 100 + 101.325
= 4.5 · 100 + 101.325
P = 551.325 kPa absolute
In the example above standard pressure being 101.325 kPa is used in the conversion, however it is
more appropriate to use the prevailing barometric pressure if known.
3.2.4. Concentration of Insulation Gases
Concentration of SF6, CF4, N2 and other insulating gases should be expressed in % volume. When
ambiguous or unclear, the gas type should also be identified.
Examples of proper usage are:
SF6 concentration: 99.98 % vol
Concentration: 99.7 % vol SF6
Concentration of the mixture: 60.2 % vol SF6, 39.8 % vol CF4
SF6/N2 concentration: 60/40 % vol
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The historical term ppmv (parts per million by volume) continues to be used widely through the industry
both as a term for decomposition products and as a unit, and is numerically equivalent to and
interchangeable with the unit µl/l.
Likewise, the historical term ppmw (parts per million by weight) is also widely used throughout the
industry both as a term for decomposition products and as a unit, and is numerically equivalent to and
interchangeable with the unit mg/kg.
It is important to recognize that conversion to/from mass-based units requires that the molecular weight
of the carrier gas, Mgas, and the molecular weight of the decomposition product, Mcontaminant, be known.
Therefore, use of mass-based units without further information regarding the specific gas (or mixture)
concentration is incomplete. The molecular weight of various gases is given in Table 3-6.
Nitrogen N2 28.01
Water H2 O 18.02
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4.2. STANDARDS
This section provides a summary of the main standards applicable to calibration and metrological
traceability.
4.2.1. ISO 9001:2015 Quality management systems – Requirements
This international standard [6] specifies requirements for a QMS when an organization:
a) needs to demonstrate its ability to consistently provide products and services that meet customer,
applicable statutory and regulatory requirements, and
b) aims to enhance customer satisfaction through the effective application of the system, including
processes for improvement of the system and the assurance of conformity to customer, applicable
statutory and regulatory requirements.
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4.2.2. ISO/IEC 17025:2005 General requirements for the competence of testing and
calibration laboratories
This is the main ISO [7] standard used by testing and calibration laboratories. In most countries,
ISO/IEC 17025 is the standard for which laboratories must hold accreditation to be considered
technically competent. In many cases, suppliers and regulatory authorities will not accept test or
calibration results from an organization that is not accredited. There are many commonalities with the
ISO 9001 standard, but ISO/IEC 17025 is more specific in requirements for competence and it applies
directly to those organizations that produce testing and calibration results.
4.2.3. ISO 17034:2016 General requirements for the competence of reference material
producers
This standard [8], that replaces ISO Guide 34:2009, specifies general requirements for the competence
and consistent operation of reference material producers. It sets out the requirements in accordance
with which reference materials (including gas mixtures) are produced. It covers the production of all
reference materials, including certified reference materials. It is intended to be used as part of the
general quality assurance procedures of the reference material producer. Reference material producers,
regulatory authorities, organizations and schemes using peer assessment, accreditation bodies and
others can also use this international standard in confirming or recognizing the competence of reference
material producers. It sets out the management system requirements in accordance with which
reference materials shall be produced. It is intended to be used as part of a reference material producer's
general quality assurance (QA) procedures.
It covers the production of all reference materials, including certified reference materials.
4.2.4. ISO/IEC Guide 98-3:2008 Uncertainty of measurement -- Part 3
This guide [9], issued by the Joint Committee for Guides in Metrology (JCGM), chaired by the Director
of the BIPM is currently the internationally agreed document on the expression of uncertainty in
measurement. It establishes general rules for evaluating and expressing uncertainty in measurement at
various levels of accuracy and in many fields, from the shop floor to fundamental research. It is
intended to be applicable to a broad spectrum of measurements, including those required for:
▪ maintaining quality control and quality assurance in production;
▪ complying with and enforcing laws and regulations;
▪ conducting basic research, and applied research and development, in science and engineering;
▪ calibrating standards and instruments and performing tests throughout a national measurement
system to achieve traceability to national standards;
▪ developing, maintaining, and comparing international and national physical reference
standards, including reference materials.
4.2.5. ISO 10012:2003 Measurement management systems
This ISO standard [10] specifies generic requirements and provides guidance for the management of
measurement processes and metrological confirmation of measuring equipment used to support and
demonstrate compliance with metrological requirements. It specifies quality management requirements
of a measurement management system that can be used by an organization performing measurements
as part of the overall management system, and to ensure metrological requirements are met. It is not
intended as a substitute for, or as an addition to, the requirements of ISO/IEC 17025.
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4.4. CALIBRATION
The outcome of a calibration is a certificate. This reports errors or corrections for an instrument and
the uncertainties in these for a given confidence level. However, obtaining calibration results with
metrological traceability is only one part of the story. The CIPM-MRA logo or the accreditation mark
of a recognized accreditation body is a guarantee of technical competence and metrological traceability
to the SI. However, it is important to understand that this applies only to the measurements performed
on the instrument under the (ideal) laboratory conditions and at the time they were made.
Having a perfect calibration certificate nicely filed for future reference if questioned, is no guarantee
that the metrological traceability chain will be maintained. The certificate is just proof that certain
measurements were performed on a given date in specific conditions, with an adequate procedure and
assigned measurement uncertainty. However, a certificate may not necessarily cover the quantities and
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ranges required by the customer´s subsequent intended use, nor be necessarily applicable in the
intended process conditions.
The certificate should contain all the information necessary to make use of the results. In the case of
certificates issued under ISO/IEC 17025, if adjustments have been performed, the values before
adjustment (as found) and the values after the adjustment (as left) will be given in the certificate.
The certificate may refer to a clearly defined specification or tolerance and may indicate compliance
or not, depending on the measured differences and the associated measurement uncertainty. However,
to get the correct calibration, the user must first be clear about the process specification and then, based
on the possible measurement uncertainty and instrument specification, decide on the extent of
calibration, and choose a calibration laboratory with the required Calibration and Measurement
Capability (CMC).
4.5.1. Pressure
Pressure is normally measured with conventional industrial pressure transmitters. These are readily
available and are easily calibrated in most industrial ISO 17025 accredited calibration laboratories with
expanded uncertainties better that 0.05 % of full scale. This is more than adequate for the level required
in SF6 measurements. Normal ranges encountered are absolute pressures from 100 kPa to 1200 kPa.
4.5.2. Temperature
The requirements for temperature measurements in SF6 can be easily achieved with common industrial
temperature sensors (platinum resistance thermometers, thermistors, thermocouples and even liquid in
glass thermometers). There are many accredited calibration laboratories that can easily provide
calibrations in the range of interest for SF6 with expanded uncertainties to ±0.10 C.
The three temperatures of interest are:
▪ Ambient temperature
▪ Enclosure temperature
▪ Gas temperature
There will generally be a temperature gradient within a compartment, so a single measurement may
not be representative of the temperature of the gas or the enclosure. With the exception of specific
installations, such as high solar gain or very low ambient temperature, measurement of temperature is
not a major concern.
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4.5.3. Density
The performance of gas insulated electrical equipment is critically dependent on the gas pressure and
therefore important that it is monitored. Since pressure in a closed vessel is temperature dependent,
density is the parameter that must be measured. Density monitors generally are mechanical pressure
gauges with mechanical temperature compensation or electronic pressure and temperature transmitters
that calculate density or direct measuring sensors measuring the variation of resonant frequency of
cavities containing the gas. The calibration needed is a combination of a traceable pressure and
temperature standards.
Some equipment used on distribution systems is ‘sealed for life’ with the gas added during assembly
in the factory and no facilities provided for gas sampling or refilling. Typically density monitors are
not fitted to this type of equipment.
4.5.4. SF6 Concentration
The traditional technique for the measurement of the SF6 content is speed of sound. The speed of sound
principle is based on evaluating the different sound velocities of gases. The main contaminant in a
compartment is generally air, which is mainly N2 and O2. Given that the speed of sound velocity in N2
and O2 is similar, it is normal to calibrate these instruments with SF6/N2 test gas. The speed of sound
in nitrogen is approximately 343 m/s and in SF6 135 m/s, at 20 °C. The typical uncertainty of these
instruments is +/−0.5 % vol SF6.
The same technique employed by a chilled mirror to measure the water vapour in SF 6 can be used to
determine the purity of the SF6 gas. Since the condensation point of pure SF6 at a given pressure is a
known value on the SF6 vapour pressure curve, the % vol SF6 can be calculated based on the difference
between the SF6 partial pressure and the measured total pressure. The typical uncertainty of these
instruments is +/−0.5 % vol SF6, and independent of the contaminants in the gas.
4.5.5. Humidity
The most common types of hygrometers are chilled mirror and polymer sensors. Chilled mirror
instruments can achieve an uncertainty of the order of 0.50 C in frost/dew-point temperature. Polymer
sensors, while considerably less expensive, can only achieve measurement uncertainties of the order
of 2 C to 3 C in frost/dew-point temperature in the same range.
4.5.6. Quantity of Substance (SF6 concentration and decomposition products)
NMIs and gas producers can produce reference gases based on ISO 17025 and ISO 17034. Example
of reference gas mixtures are can be found in [7] and [8]
▪ Primary Reference Gas Mixtures (PRGM): These have the lowest available uncertainty and are
prepared gravimetrically in accordance with international Standard ISO 6142-1:2015 [13], only
applicable to mixtures of gaseous or totally vaporised components, which may be introduced into
the cylinder in the gaseous or liquid state. Both binary and multi-component gas mixtures
(including SF6) are covered by this part of ISO 6142. The producer usually validates these against
Primary Standard Gas Mixtures. The certificate provided reports the gravimetric value with an
uncertainty that represents the best achievable analytical uncertainty. It also contains an expiry
date for the mixture, which is assigned from data obtained from stability studies of similar
mixtures.
▪ Calibrated Gas Mixtures (CGM). These are mixtures that have been supplied by customers to an
accredited laboratory or NMI and individually certified against PRGM using advanced analytical
methods. The certificate provided gives the value determined by the analytical method used, and
an analytical uncertainty (which is typically larger than that provided for a PRGM). A stability
guarantee is not normally given for a CGM due to a lack of knowledge of the history of the cylinder
and the gas mixture.
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▪ Secondary Gas Standards (SGS). These mixtures, which typically contain reactive and unstable
components, are prepared gravimetrically, and are provided with a certificate that reports the value
obtained from the analytical certification process with an appropriate measurement uncertainty.
These do not have a guarantee of stability.
Calibrated gas mixtures are required to ensure measurement traceability for test instruments [14]. For
the calibration of the purity measurement, traceable gas mixtures are used. These gas mixtures contain
SF6 with a known amount of nitrogen (N2). Because of the vapour pressure of SF6 the max pressure of
these mixtures is limited. The typical uncertainty of these gas mixtures is +/−2 % relative.
Calibration gas mixtures containing SF6 decomposition products are much more challenging to
produce and have higher uncertainty than inert gas mixtures. The typical uncertainty of these gas
mixtures is +/−5% relative. Calibration gases with SO2 in SF6 are quite common. While gas mixtures
containing HF or SF4 are not available for calibration purposes.
Instruments can be calibrated with different references gases, for instance SO2 in nitrogen. However,
an instrument calibrated with this reference gas will not provide accurate results when measurements
are made with SF6. Users need to verify what reference gas was used for calibration.
It is not possible to produce SF6 gas with a defined humidity level and therefore calibration is normally
performed in air or nitrogen using a standard humidity generator. The traceability in humidity
measurements can be obtained in numerous NMIs and DIs signatories to the CIPM-MRA and by ISO
17025 accredited calibration laboratories.
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SF6 MEASUREMENT GUIDE
The second edition of IEC 60376 [15] is a technical revision of the first edition published in 1971, its
first supplement IEC 60376A (1973) and its second supplement IEC 60376B (1974). It differs widely
from the first edition. In 1970’s when the SF6 technology was still new, the target was to ensure that
the best possible quality SF6 was used in electric equipment. By early 2000’s, the SF6 technology had
reached maturity and the approach to SF6 quality changed from one of trying to achieve the highest
quality possible to one of ensuring adequate quality to guarantee the required performance of the
electric equipment. As a direct consequence, the term used to identify this gas quality was changed
from “new” to “technical grade” and the acceptable impurity and contaminant level were increased
based on experience gained over 30 years. When used in electric equipment “technical grade SF6”
behaves like the former “new SF6”.
The second edition of IEC 60480 [16] is a technical revision of the first edition published in 1974. In
1970’s when the SF6 technology was still new, the target was to give guidance for checking of sulphur
hexafluoride taken from electric equipment. With the maturing of SF6 technology, environmental
concerns became the priority and the focus was to avoid the release of gas during handling of SF6 and
the development of the concept of a “closed cycle”. The maximum contamination level in “reuse SF6“,
recovered from electric equipment (i.e. “used SF6 suitable for reuse on site” as per IEC 62271-4 clause
2.15) was defined and therefore facilitates the re-use of gas. The basis for this revision to the IEC was
the CIGRÉ Technical Brochure no. 234 [17].
The quality requirements for “used SF6 suitable for reuse on site” are lower than the quality
requirements for “technical grade SF6”, nevertheless as clearly described in the CIGRÉ Technical
Brochure no. 234, the quality of is still adequate to be used in electric equipment without impairing the
performance of the equipment even in the long term.
Table 5-1 compares “technical grade SF6” (IEC 60376), “used SF6 suitable for reuse on site” (IEC
60480), and the CIGRÉ proposal in the Technical Brochure no. 234. The two standards and the CIGRÉ
Technical Brochure make use of different units (e.g. ppmv, mg/kg) to express concentration. The
figures in Table 5-1 have been converted to so that all concentrations are given in µl/l.
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SF6 MEASUREMENT GUIDE
Table 5-1 Comparison among “technical grade SF6” (IEC 60376), “used SF6 suitable for reuse on
site” (IEC 60480), and the CIGRÉ proposal in the Technical Brochure no. 234. All quantities have
been converted to the same units.
Typical
Technical SF6
IEC 60376 IEC 60480 CIGRÉ no. 234
gas
Contaminant
Specification
Rated Rated Rated Rated
All absolute absolute absolute absolute
All pressures
pressures pressure pressure pressure <200 pressure
<200 kPa >200 kPa kPa >200 kPa
Air 1% vol not given not given not given not given 250 µl/l
CF4 0.4% vol not given not given not given not given 20 µl/l
Air and/or CF4 not given 3% vol 3% vol 3% vol 3% vol not given
Humidity 200 µl/l 750 µl/l 200 µl/l 750 µl/l 200 µl/l 5 µl/l
Acidity in HF 7 µl/l 25 µl/l 25 µl/l 25 µl/l 25 µl/l 2 µl/l
Mineral oil 10 mg/kg 10 mg/kg 10 mg/kg use oil trap use oil trap 1 mg/kg
With the exception of mineral oil, which according to CIGRÉ can be reduced far below the IEC limit
just using an oil trap, IEC 60480 specifies the same maximum acceptable contamination levels as
proposed by CIGRÉ.
It is interesting to note that the second revision to IEC 60480 was published before the second revision
to IEC 60376. This was done to establish limits for “used SF6 suitable for re-use” before establishing
the limits for technical grade SF6.
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SF6 MEASUREMENT GUIDE
6. HUMIDITY
6.1. IDEAL GAS LAW AND VAPOUR PRESSURE CURVE
Before reading the next section, readers may find it beneficial to review the concepts of the Ideal Gas
and the SF6 vapour pressure curve, summaries of which are provided in Appendix A.
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SF6 MEASUREMENT GUIDE
Based on the above data, it is evident that the change in frost or dew point due to a change in the
compartment temperature is quite small (approximately 1 °C frost point change for every 30 °C
temperature change) in a non-hygroscopic compartment.
In practice, however, switchgear compartments contain many hygroscopic components (insulators,
actuators, the inner vessel walls and other surfaces) that adsorb/absorb/desorb water vapour as a
function of temperature. This adsorption/absorption/desorption is a significant factor within SF6
vessels, completely dominating the normal thermo-physical gas behaviour.
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SF6 MEASUREMENT GUIDE
much effort is made to control humidity during initial manufacture, assemble, commissioning and over
the lifetime of the equipment.
Equally well known is the phenomenon of moisture transfer between the gas and the internal surfaces
of the enclosure and the polymeric materials within the enclosure due to temperature fluctuations. As
the temperature of the enclosure and insulating material increases more moisture is transferred to the
gas, with the process reversed as the enclosure cools. This effect of temperature is not fundamental and
depends substantially on the hygroscopic nature of the encasing materials, the surface areas, the
presence of absorbers and the effectiveness of compartment evacuation prior to filling. The process of
adsorption and absorption is illustrated in Figure 6-1.
Figure 6-1 Adsorption and Absorption of Water Molecules
Although these absorption/adsorption/desorption effects are measurable, they differ significantly from
vessel to vessel, and design to design, due to differences in the quantity and composition of the internal
materials used.
This change in humidity levels raises several issues:
How to differentiate between an underlying change in humidity and this temperature induced
effect,
The specific impact of humidity on dielectric withstand capability (and the relationship to
number of molecules of H2O (μl/l ) versus relative humidity (% rh),
The level of humidity that should not be exceeded in order to avoid the formation of
corrosive decomposition products.
Several different approaches have been adopted to deal with this temperature induced effect. Some
users have sought to develop “normalization” process that seeks to factor out the effect. Some have
gone so far as to code in correction factors in hydrometers so that a correction is applied automatically
to the measured value. However other users do not use this approach.
Recently the option of using relative humidity (U), which is itself inherently temperature (and pressure)
dependent, has been proposed as a measure of humidity. Long-term tests were carried out on individual
GIS compartments to monitor the variation in humidity over time and versus temperature. When the
measurand is expressed as a volume fraction (either ppmv or μl/l) the values vary widely with
temperature, while if it is expressed as % rh, the variation is more limited thereby appearing to remove
the temperature induced effect on humidity [19]. While this method has a major practical benefit, the
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SF6 MEASUREMENT GUIDE
concern remains that, while %rh can remain constant, the number of water molecules in the gas will
increase. The question is what is the impact on breakdown voltage across a spark gap or along an
insulator surface as the humidity increases?
However, what has become clear over the last few years is the need to better control humidity, which
has led to the almost universal application of absorbers in gas compartments (and not just
compartments containing switching elements) and more stringent controls during switchgear assembly
and subsequent maintenance activities.
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SF6 MEASUREMENT GUIDE
To avoid these concerns, some manufacturers recommend that measurements are not performed in low
ambient temperatures. However, this approach may not always be possible, particularly when the
equipment is located in a cold climate.
Furthermore, when condensation has occurred within a gas compartment at low temperature, and the
ambient temperature later rises, it is unknown if all the ice will fully sublime during the temperature
rise. It is possible, depending on the rate of temperature rise of the compartment, that some ice may
still be present as the temperature rises above 0 °C. As the compartment temperature crosses 0 °C, any
remaining ice will melt into liquid water. This effect is potentially dangerous and works against the
original idea of setting an upper humidity limit of −5 °C frost point temperature at the temperature of
the compartment.
6.9.4. New concepts for recommended humidity limits
A degree of confusion exists within the industry arising from the misunderstanding of the impact of an
internal pressure change (due to a temperature change) on the frost/dew point temperature and the
adsorption/desorption phenomenon. There is also a degree of frustration within utilities, who are tasked
with maintaining the equipment, as to how to adequately assess the reliability of their equipment in the
presence of fluctuating humidity levels due to temperature variations.
6.9.4.1. ∆t concept
When a need exists to perform measurements in ambient temperatures below +5 °C, a ∆t of 10 °C
should be adopted for determining the maximum allowable frost point temperature. As an example, if
the ambient temperature at the time of measurement is −12 °C, the measured frost point (at
compartment pressure) should be −22 °C or lower. This ensures that condensation has not occurred
within the compartment, thus there is no risk of liquid water due to melting.
In certain climatic situation, in particular those that can experience very low temperatures, a ∆t of 10 °C
may not be appropriate and a larger value should be selected. Some utilities use a ∆t of 20 °C to provide
a greater margin.
6.9.4.2. Relative humidity concept
Taking this concept of a ∆t it is possible to calculate the equivalent relative humidity value for a range
of gas compartment temperatures. A further advancement is to consider a number of values for ∆t (the
larger the value the more conservative the approach) and calculate the equivalent relative humidity
values. The results of this exercise for three values of ∆t and four values of gas compartment
temperature are given in Table 6-2.
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SF6 MEASUREMENT GUIDE
This table provides the equivalent relative humidity values for different ∆t values at different
compartment temperatures. Increasing the value of ∆t provides a greater safety margin that is similarly
reflected in the relative humidity values, which reduce as ∆t increases.
6.9.5. Conclusion
The sections above outline a new approach to the measurement of humidity especially at low
temperatures, introducing the concept of a “∆t”.
This new concept may also have implications for humidity levels in equipment in regions with tropical
temperatures. In these regions as the ambient temperature never approaches zero, setting a frost point
limit of −5 °C may be overly conservative and therefore adopting the “∆t” may be more appropriate.
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SF6 MEASUREMENT GUIDE
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and rapidly reacts with the metal oxides on the surface material making it short lived compared to other
decomposition products. The metal fluorides remain as powder or dust on the surface. H2O is released
in this reaction and therefore available for further reactions with SF4 or for the much slower conversion
of SOF2 to SO2. In this process, H2O is in fact not consumed but plays the role of a catalyst.
Figure 7-1: Schematics of hot plasma reactions (left side) and cold wall reactions (right side)
Al2O3
FeO
Cu
SF6 ® SFx + (6 - x) F Al
W SF4 + H 2O ® SOF2 + 2HF
SF6 + Cu ® CuF2 + SF4 PTFE SO2F2
2 HF + FeO ® FeF2 + H 2O
3SF6 + W ® WF6 + 3SF4
SOF2 6 HF + Al 2O3 ® 2 AlF3 + 3H 2O
3SF6 + 2 Al ® 2 Al F3 + 3SF4
SF4 H2 O 4HF + SiO2 ® SiF4 + 2H 2O
2 F + CF2 ® CF4 ARC
SF6
SOF4 + H 2O ® SO2 F2 + 2HF
H + F ® HF
HF SOF2
SF4 + O ® SOF4 SOF2 + H 2O ® SO2 + 2HF
SO2
SF2 + O2 ® SO2 F2 2 HF SOF4 + SF6 ® S2OF10
Electrode
FeF2
2 HF
AlF3
2 HF
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SF6 MEASUREMENT GUIDE
surface reaction of SF4 with water molecules as well as in the subsequent decomposition of SOF2 with
humidity, thereby producing SO2 as a final stable decomposition product. Humidity is a pre-requisite
for this decomposition process that in practice is always available on the surfaces.
In fact HF is mainly observed where a high concentration of SF4 itself is detected e.g. shortly after a
short-circuit interruption. High concentrations of SF4 (in the range of 1000 ppmv and higher) may
remain in a large compartment for several hours or even days after a switching event. In-situ gas
analysis, if done during this time, may detect HF. As the SF4 is eliminated, so also is the HF.
The relative abundance of HF is difficult to determine since the reaction speeds or rates of formation
of the three decomposition products SF4 i.e. HF, SOF2 and SO2 are very dissimilar. Although the
decomposition of SF4 into SOF2 and HF should deliver 1 part of SOF2 and 2 parts of HF, the
concentration of both parts in the gas volume does not obey a ratio of 1:2. Since the subsequent reaction
of SOF2 with water into SO2 takes much longer than the subsequent reaction of HF with metal oxides,
SOF2 will accumulate in the volume whereas HF will diminish. Therefore, the concentration of SOF 2
in the gas will be much higher than that of HF. The amount of HF produced by the conversion of SOF2
into SO2 is even lower, since the reaction speed of this process is low compared to that of SF4.
One consequence of the high reactivity of HF is that, on its own, it is not a good indication of the
volume of decomposition products created. Considering the reaction schemes other decomposition
products provide more reliable indication, e.g. SO2. However, if a suitable method for measuring HF
becomes available, this test might add value to the diagnosis.
7.4.3. CF4
Most of the SF6 insulated circuit breakers and load switches use nozzles made of PTFE for current
interruption or breaking. Its main decomposition product, when in contact with an SF6 arc, is CF4 (see
Figure 7-1). These nozzles serve to shape the flow of cold gas and hot arc plasma to cool the arc by
heat removal while increasing the gas pressure and facilitate arc extinction. With each current
interruption ablation of nozzle material occurs with the result that the nozzle diameter increases and its
performance deteriorates over time.
7.4.4. Metal Fluorides
Solid decomposition products (mainly metal fluorides and metal oxide fluorides) may be produced
directly by the interaction of an arc with metal parts or by the reaction of decomposition products of
SF6 with metals or metal oxides. The main decomposition products are AlF3, CuF2 and WF6.
AlF3 is produced by the interaction of an arc with aluminium or by the reaction of HF with Al2O3 e.g.
at the inner wall of a compartment. This white powder is usually the main solid product found after
electrical activity in a compartment. CuF2, which is also a white powder, is produced by the interaction
of an arc with copper or components containing copper. WF6 is produced by the interaction of an arc
with the material of the main contact. It is very toxic and has special physical properties. Above 17 °C
it exists in the form of a colourless gas, between 2 °C and 17 °C it is a pale yellow liquid and below
2 °C it freezes into a white solid. WF6 reacts instantaneously with water to form H2WO4 and HF.
The amount of metal fluorides produced by an arc cannot be determined quantitatively. Metal fluorides
and their further reaction products are non-conductive and therefore do not reduce the dielectric
insulation levels.
For removal, the compartment must be opened and partly disassembled and all surfaces must be
cleaned carefully. Metal fluorides cannot be detected by gas analysis.
7.4.5. Other Contaminants
Discharge or abnormal heating of polymeric materials like epoxy insulators or cellulose insulating
material, as used in instrument transformer windings, may produce CO or CO 2. Similarly, COS may
be produced by corona discharge involving polymer material.
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SF6 MEASUREMENT GUIDE
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SF6 MEASUREMENT GUIDE
Measuring SF6 gas quality in-service is essential when deciding if corrective actions are needed to
ensure the correct performance of equipment and prevent failure. The most common measurements
are performed during the operational life of equipment and this section focuses specifically on this
important task.
Gas measurements are also required following an internal fault in the equipment, however in this
situation the focus is generally on identifying the specific compartment where the fault occurred and
to identify the safety precautions required to be taken by site personnel [27].
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SF6 MEASUREMENT GUIDE
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SF6 MEASUREMENT GUIDE
Within the EU, specific training for the handling of SF6 gas is also required, F-Gas Regulation [29].
It is often possible to save specific configurations for later recall and use. Users should refer to the
instruction manual for guidance.
8.6.2. Gas Recovery and Pump Back
The process of gas quality measurement should not result in the release of any SF6 to the atmosphere.
Modern instruments collect the gas during measurement and pump it back into the compartment
when the measurement is completed. This feature may be integrated within the instrument, or may
require connection to a separate gas recovery system.
The pump back process may be initiated automatically within the measurement procedure, or carried
out manually. Refer to the instruments user manual for guidance.
If the intention is to repeat the gas measurement immediately, then the gas should not be pumped
back into the compartment until all measurements are completed so as to avoid repeat testing of the
same gas sample.
8.6.3. SF6 Gas Analyser Performance and Calibration Verification
It is important that the performance of the analyser to be used matches the accuracy and range
requirements of the tests.
Modern SF6 gas analysers feature self-test or calibration check functions that may be useful in
determining the performance of the instrument at a specific point in time. Users should refer to the
analyser instruction manual for specific guidance.
8.6.4. Sampling Hoses
Sampling hoses are the cause of many of the issues encountered during on-site measurements. The
following information explains the importance of appropriate sampling hose design and maintenance.
8.6.4.1. Sampling Hose Material
Portable analysers make use of a flexible sampling hose to provide a connection from the gas
compartment to the analyser. In most cases the sampling hose is not permanently fixed to the
analyser and is disconnected after use.
A steel braided outer sheath normally protects the sampling hose from damage. To perform accurate
humidity measurement in the gas compartment, the quality of the sampling path is critical. For this
45
SF6 MEASUREMENT GUIDE
reason, the sampling hose should be constructed from a non-hygroscopic material such as PTFE.
Rubber hoses should not be used due to their hygroscopic properties and high permeability to water
vapour. The length of the hose and the internal diameter (e.g. inner surface area) should be kept to a
minimum. Lengths of 3 to 6 meters are recommended but longer lengths may have to be used for
sampling points that are located at elevated positions on the equipment.
8.6.4.2. Sampling Hose Couplings
The sampling hose should be equipped with self-closing couplings at both ends to prevent the escape
of gas from the compartment and to avoid the ingress of humidity into the hose. This ensures that
when the hose is disconnected from the gas compartment or analyser, the ends of the hose close
automatically.
Similarly, all valves on gas compartment should be self-closing. The use of adaptor fittings between
the gas compartment and the sampling hose should be avoided to minimize risk of leaks and
minimize residual humidity effects.
8.6.4.3. Sampling Hose Purge
Generally there is no requirement to purge sampling hoses, however should such a requirement arise
then the gas used to purge the hose should be collected and not released to atmosphere.
8.6.4.4. Sampling Hose Evacuation
The SF6 analyser or a vacuum pump can be used to evacuate the sampling hose prior to the
measurement. This procedure is normally carried out with the sampling hose disconnected from the
electrical equipment (and any manufacturer’s instructions in this regard should be strictly followed).
The evacuation is intended to pre-condition the sampling hose when contamination by air is a
concern.
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SF6 MEASUREMENT GUIDE
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SF6 MEASUREMENT GUIDE
It is recommended that this order is followed to avoid inadvertent damage to a measuring instrument
due to excessive levels of decomposition products. Some instruments include sensors or components
that may be damaged by high concentrations of decomposition products, so refer to instruction
manual or the manufacturer for guidance before measurement.
The flowcharts provide a pictorial view of the analysis and decision-making process. It is assumed that
all measurements are carried out at an ambient temperature higher than the dew/frost point temperature
of the gas.
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SF6 MEASUREMENT GUIDE
Figure 8-1: Decision making process for SF6 gas analysis to identify decomposition products
If
If internal
internal arcing
arcing suspected,
suspected, initially
initially use
use
SO
SO22 detector
detector tubes
tubes ifif electronic
electronic
SF
SF66 Gas
Gas Analysis
Analysis instrument does not have an
instrument does not have an automatic automatic
decomposition
decomposition shut
shut down
down oror ifif instrument
instrument willwill be
be
products
products dameged
dameged by by excessive
excessive levels
levels of
of
decomposition products
decomposition products
SO
SO22 No
detected
detected
Yes
Check
Check test
test procedure/device
procedure/device
Retest
Retest
SO
SO22 No
detected
detected
Yes
Switching
Switching No Immediate
Immediate action
action
Compartment
Compartment required
required
Yes
Retest
Retest after
after several
several
hours
hours or
or days
days
SO
SO22 No
detected
detected
Yes
No Do
Do manufactures
manufactures
specify
specify limits?
limits?
Yes
No Take
Take action/contact
action/contact
Within
Within limits?
limits? manufacturer
manufacturer
Yes
Compare
Compare results
results between
between Monitor
Monitor level
level of
of
phases,
phases, with
with similar
similar Significant
Significant No decomposition
decomposition products,
products, No SF
SF66 Gas
Gas Analysis
Analysis
compartments
compartments // number
number ofof difference
difference initiate
initiate action
action ifif Humidity
Humidity
operations
operations // loading
loading history
history increasing
increasing
Yes
Immediate
Immediate action
action
required
required // contact
contact
manufacturer
manufacturer
49
SF6 MEASUREMENT GUIDE
Figure 8-2: Decision making Process for SF6 Gas Analysis to identify Humidity
Yes
Yes
Yes
Figure 8-3: Decision making Process for SF6 Gas Analysis to identify SF6 Concentration
SF
SF66 Gas
Gas Analysis
Analysis
SF
SF66 Concentration
Concentration
No Investigate
Investigate reason
reason for
for
SF
SF66 >> low
low SF
SF66 content
content
minimum
minimum limit
limit Correct
Correct SF
SF66 content
content
Yes
Record
Record SO
SO22,,
Humidity,
Humidity,
SF
SF66 Concentration
Concentration
50
SF6 MEASUREMENT GUIDE
𝑘⋅𝑅⋅𝑇 (1)
𝑎=√
𝑀
a = speed of sound
k = isentropic exponent ratio of heat capacity
𝑇 = temperature in Kelvin
𝑅 = gas constant (8.3145 J/mol ·K)
M = molecular mass (kg/mol)
𝐽
8.3145 ⋅ 1.0952 ⋅ 293.5 𝐾 𝑚
𝑎𝑆𝐹6 =√ 𝑚𝑜𝑙 ⋅𝐾 = 135.19
𝑘𝑔 𝑠 (2)
0.146055
𝑚𝑜𝑙
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SF6 MEASUREMENT GUIDE
The speed of sound for a gas mixture is derived as follows, consider 50% SF6 (x=0.5) and 50% N2
(y=0.5):
𝑅 ⋅ 𝑥 ⋅ 𝑘𝑎 + 𝑦 ⋅ 𝑘𝑏 ⋅ 𝑇
𝑎𝑚𝑖𝑥 = √ , with x + y = 1
𝑥 ⋅ 𝑀𝑎 + 𝑦 ⋅ 𝑀𝑏
𝐽
8.3145 ⋅ 0.5 ⋅ 1.0952 + 0.5 ⋅ 1.3996 ⋅ 293.15 𝐾 𝑚
𝑎𝑚𝑖𝑥 ,50/50 = √ 𝑚𝑜𝑙 ⋅ 𝐾 = 186.90 (3)
𝑘𝑔 𝑘𝑔 𝑠
0.5 ⋅ 0.146055 + 0.5 ⋅ 0.0280134
𝑚𝑜𝑙 𝑚𝑜𝑙
For binary gas mixtures with an impurity, the speed of sound is derived as follows:
𝑅 ⋅ 𝑥 ⋅ 1 − 𝑧 ⋅ 𝑘𝑎 + 𝑦 ⋅ 1 − 𝑧 ⋅ 𝑘𝑏 + 𝑧 ⋅ 𝑘𝑧 ⋅ 𝑇 𝑅 ⋅ 𝑥′ ⋅ 𝑘𝑎 + 𝑦′ ⋅ 𝑘𝑏 + 𝑧 ⋅ 𝑘𝑧 ⋅ 𝑇
𝑎𝑚𝑖𝑥 = √ =√
𝑥 ⋅ 1 − 𝑧 ⋅ 𝑀𝑎 + 𝑦 ⋅ 1 − 𝑧 ⋅ 𝑀𝑏 + 𝑧 ⋅ 𝑀𝑧 𝑥 ′ ⋅ 𝑀𝑎 + 𝑦 ′ ⋅ 𝑀𝑏 + 𝑧 ⋅ 𝑀𝑧
with 𝑥 ′ + 𝑦 ′ + 𝑧 = 1, 𝑥 ′ = 𝑥 ⋅ 1 − 𝑧 , 𝑦 ′ = 𝑦 ⋅ 1 − 𝑧 , 𝑥, 𝑦, 𝑧 ∈ [0,1]
(4)
If the impurity is air, then:
𝑐𝑝
𝑘𝑖 = isentropic exponent ratio of heat capacity (𝑘 = ) [33] [34].
𝑐𝑣
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SF6 MEASUREMENT GUIDE
When the contaminant is air and the level of contamination is low, typically associated with a gas
handling or gas leakage problem, then the measurement of the speed of sound can be used to
determine the content of SF6 and N2. Essentially the introduction of air has not changed the binary
gases as air is mainly N2. However, this does not apply when the binary gases are SF6 and CF4.
Consider the example where the initial ratio is 50 % SF6 / 50 % CF4, which results in a speed of
sound of 153.24 m/s. If we now introduce 1% air and recalculate the speed of sound the result is
amix,20°C = 154 m/s. However, this is not a unique solution. Consider a gas mixture with a ratio
57.56 % SF6 and 42.44 % CF4 with a contamination of 5 % air, the speed of sound for this mixture is
again amix,20°C = 154 m/s.
Effectively we have three unknowns and only one measurement parameter, therefore you cannot
determine the quantity of the individual gases.
8.9.2. Practical Examples and Experience
Table 8-2 and Table 8-3 show the substantial errors in the value of SF6 that can result when using an
instrument that has been calibrated based on a pre-defined gas mixture.
The theoretical SF6 (Xapp) concentration follows from equation 3:
𝑅 ⋅ 𝑥 ⋅ 𝑘𝑎 + 𝑦 ⋅ 𝑘𝑏 ⋅ 𝑇 𝑅 ⋅ 𝑥 ⋅ 𝑘𝑎 + 1 − 𝑥 ⋅ 𝑘𝑏 ⋅ 𝑇
𝑎𝑚𝑖𝑥 = √ ⇔ 𝑎𝑚𝑖𝑥 = √ (5)
𝑥 ⋅ 𝑀𝑎 + 𝑦 ⋅ 𝑀𝑏 𝑥 ⋅ 𝑀𝑎 + 1 − 𝑥 ⋅ 𝑀𝑏
2
𝑎𝑚𝑖𝑥 ⋅ 𝑀𝑏 − 𝑇 ⋅ 𝑅 ⋅ 𝑘𝑏
⇒ 𝑥 = 𝑋𝑎𝑝𝑝 = 2
𝑎𝑚𝑖𝑥 ⋅ 𝑀𝑏 − 𝑀𝑎 + 𝑇 ⋅ 𝑅 ⋅ 𝑘𝑎 − 𝑘𝑏
Table 8-2 Mixture of SF6/CF4 50/50%. Impact of air contamination on the measurement of SF6
concentration when measuring with a portable instrument
Theoretical
Sound speed Total Sound Real SF6 with SF6
SF6
Air without speed with contamination reading on
Variation
contamination contamination (x’) portable
instrument
%
m/s m/s % volume % volume
volume
1% 153.24 154.00 49.50 48.21 –1.290
2% 153.24 154.77 49.00 46.43 –2.573
5% 153.24 157.14 47.50 41.08 –6.415
10 % 153.24 161.26 45.00 32.28 –12.719
In the case of a mixture of SF6/CF4 (50/50), the difference between the theoretical calculation of SF6
and the actual percentage of SF6 in the presence of contamination is substantial. In fact, the
calculated quantity of SF6 will be underestimated by approximately 1.3 % for each 1 % in volume of
air contamination.
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Table 8-3 Mixture of SF6/N2 50/50%. Impact of air contamination on the measurement of SF6
concentration when measured with a portable instrument
Theoretical
Sound speed Total Sound Real SF6 with SF6 SF6
Air without speed with contamination reading on Variation
contamination contamination (x’) portable (Xapp−x’)
instrument
%
m/s m/s % volume % volume
volume
1 186.90 187.65 49.50 49.50 0.003
2 186.90 188.39 49.00 49.02 0.016
5 186.90 190.68 47.50 47.53 0.035
10 186.90 194.65 45.00 45.07 0.067
In the case of a mixture of SF6/N2 (50/50), the difference between the theoretical calculation of SF6
and the actual percentage is less pronounced. In this case, the calculated amount of SF6 will be
overestimated by about 0.006 % for each 1 % volume of air contamination.
However somewhat more worrying is that actual measurements with portable instruments have been
shown to have an even greater error between the displayed and actual quantity of SF6.
Such underestimation of the proportion of SF6 concentration can lead to inappropriate “topping up”
with SF6, which in turn may have an impact on device performance including liquefaction of SF6
during low temperature conditions.
8.9.3. Conclusion
When there is concern that a third gas, a contaminant, has been introduced into an enclosure
containing an SF6/CF4 mixtures, the only reliable and accurate measurement of gas percentage is to
use gas chromatography, which must be done in a laboratory. Portable instruments are calibrated
against known gas mixtures and therefore they will give incorrect readings if used to measure
different gas mixtures or if a contaminant is present in the gas mixture.
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9. CONCLUSIONS
This guide focuses on the practical aspects of undertaking on-site measurements of SF6 gas parameters
to ensure the most reliable results possible. It examines all aspects of the measurement system from
the analyser to the sampling hoses, connections and critically, the management of the gas sample. Once
the measurements have been made, it provides guidance on how to interpret the results and what are
the most appropriate actions.
Furthermore, it explores the potential complications involved when trying to take measurements at low
ambient temperature or when gas mixtures are involved. It provides suggestions as to how these
complications can be mitigated.
The final item considered is the use of the historic frost-point temperature limit of −5 °C, at
compartment pressure. While this limit has proved itself effective over many years of use, the
requirement to normalize the results to 20 °C has been controversial and indeed confusing. In the
brochure, we disentangle the two phenomena that cause the humidity level in the gas to change with
temperature and show that the absorption/desorption phenomenon totally dominates. We identify an
alternative humidity limit that some users may find beneficial when faced with operating equipment at
very cold ambient temperatures.
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10. REFERENCES
[1] IEC 60050 International Electrotechnical Vocabulary Series.
[2] ISO/IEC Guide 99:2007 International vocabulary of metrology - Basic and general concepts and
associated terms (VIM). http://www.iso.org/sites/JCGM/VIM-introduction.htm.
[3] ISO/IEC Guide 98-3:2008 Uncertainty of measurement - Part 3: Guide to the expression of
uncertainty in measurement (GUM:1995). http://www.iso.org/sites/JCGM/GUM-
introduction.htm.
[4] BIPM Bureau International des Poids et Mesures.
[5] SI Brochure : The International System of Units (SI) [8th edition, 2006; updated 2014]
[6] ISO 9001:2015 Quality management systems – Requirements.
[7] ISO/IEC 17025:2005 General requirements for the competence of testing and calibration
laboratories.
[8] ISO 17034:2016 General requirements for the competence of reference material producers.
[9] ISO/IEC Guide 98-3:2008 Uncertainty of measurement -- Part 3: Guide to the expression of
uncertainty in measurement (GUM:1995).
[10] ISO 10012:2003 Measurement management systems - Requirements for measurement processes
and measuring equipment.
[11] CIPM-MRA Mutual recognition of national measurement standards and of calibration and
measurement certificates issued by national metrology institutes, 1999. (Modified by the CIPM,
2003). http://www.bipm.org/en/cipm-mra/cipm-mra-documents/.
[12] The ILAC Mutual Recognition Arrangement.
[13] ISO 6142-1:2015 Gas analysis - Preparation of calibration gas mixtures - Part 1: Gravimetric
method for Class I mixtures.
[14] ISO 6143:2001 Gas analysis - Comparison methods for determining and checking the
composition of calibration gas mixtures. Last reviewed in 2011.
[15] IEC 60376:2005 Specification of technical grade sulphur hexafluoride (SF6) for use in electrical
equipment.
[16] IEC 60480:2004 Guidelines for the checking and treatment of sulphur hexafluoride (SF6) taken
from electrical equipment and specification for its re-use.
[17] CIGRÉ Technical Brochure No 234 SF6 Recycling Guide (revision 2003).
[18] IEC 62271-1:2007+AMD1:2011 CSV Consolidated version. High-voltage switchgear and
controlgear - Part 1: Common specifications.
[19] Lessard M-C, Larocque G, Gendron S, Laberge S, Lavoie Y, A New Approach for Assessing
the Moisture Content in SF6 Insulated Equipment, 2016 Electrical Insulation Conference,
Montreal, Quebec, Canada, 19 – 22 June 2016.
[20] D. H. Peng, Z. Y. Li and J, M. K. MacAlpine, The Combined Effect of Moisture, Temperature
and Conducting Particles on the Discharge Behaviour of Sulphur Hexafluoride, 1999 Conference
on Electrical Insulation and Dielectric Phenomena.
[21] CEATI International Report 217-T-424, 1989, Canadian Electrical Association.
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APPENDICES
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The following example illustrates the change in pressure with changing temperature in a closed vessel.
At a measured pressure of 500 kPa and measured temperature of 50 °C, the corresponding change in
pressure as the vessel is cooled to a temperature of 20 °C is calculated as follows:
P1 = 500 kPa
t1 = 50 °C
t2 = 20 °C
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regardless of temperature induced pressure changes. Although frost/dew point is not temperature
dependent by definition, the total pressure and the water vapour partial pressure within a non-
hygroscopic closed vessel are temperature related. As temperature increases or decreases, the total
pressure and water vapour partial pressure increase or decrease proportionately, resulting in a change
of frost/dew point due only to the pressure variation. This effect only applies to frost/dew point
measurements made at compartment pressure.
As seen in an example in Appendix A.2 Temperature Induced Pressure Change in a Closed Vessel, an
initial pressure of 500 kPa, initial temperature of 50 °C and final temperature of 20 °C results in a final
pressure of 454 kPa. Now, if we assume an initial frost point of –30 °C measured at vessel pressure,
compute the corresponding frost point if the vessel were cooled to a final temperature of 20 °C.
P1 = 500 kPa
T1 = 50 °C
T2 = 20 °C
22.46 ∙ 𝑡f1
𝑒1 = 611.2 ∙ exp ( )
272.62 + 𝑃1
With the reverse vapour pressure equation and vapour pressure e2, calculate frost point temperature tf2
relative to pressure p2.
𝑒2
ln (
)
𝑡f2 = 272.62 611.2
𝑒
22.46 − ln ( 2 )
611.2
22.46 ∙ −30
𝑒1 = 611.2 ∙ exp ( ) = 38.02
272.62 + −30
454
𝑒2 = ∙ 38.02 = 34.53
500
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34.53
ln ()
𝑡f2 = 272.62 611.2 = −31 °C
34.53
22.46 − ln ( )
611.2
The frost point tf2 at the vessel pressure P2 of 454 kPa absolute is −31 °C. Therefore, starting with a
measured frost point of -30 °C at a vessel pressure of 500 kPa and vessel temperature of 50 °C, a non-
hygroscopic vessel will decrease to a frost point of -31 °C at a pressure of 454 kPa due solely to a
decrease in vessel pressure as a result of a decrease in vessel temperature to 20 °C.
This small change in the frost point due to a large change in the vessel temperature (which resulted in
a pressure change, which ultimately resulted in a frost point change) is a typical example of the thermo-
physical gas properties as applied to a non-hygroscopic vessel. As seen from the example, the frost/dew
point change, due to this vessel temperature change, is typically very small (approximately 1/30).
In reality however, vessels used for SF6 contain many hygroscopic components (insulators, actuators,
the inner vessel walls and other surfaces) that adsorb/absorb/desorb water vapour as a function of
temperature. This absorption/adsorption/desorption is a significant factor within SF6 vessels,
completely dominating the normal thermo-physical gas behaviour.
Temperature [°C] –50 –45 –40 –35 –30 –25 –20 –15 –10 –5
SF6 Vapour
227.5 279.8 340.8 411.4 492.4 584.7 689.4 807.4 939.7 1087.5
Pressure [kPa]
Temperature [°C] 0 5 10 15 20 25 30 35 40 45
SF6 Vapour
1251.7 1433.5 1634.2 1855.1 2097.7 2363.5 2654.5 2973.0 3322.1 3707.7
Pressure [kPa]
The SF6 vapour pressure, 𝜌𝜎 , may also be computed with the following formula.
𝜌𝜎 𝑡𝑐 + 273.15
ln ( )=( ) ∙ 𝑁1 𝜏 + 𝑁2 𝜏 1.5 + 𝑁3 𝜏 2 + 𝑁4 𝜏 4
𝑝𝑐 𝑡 + 273.15
or, rewritten as
𝑡 +273.15
[( 𝑐 )∙(𝑁1 𝜏+ 𝑁2 𝜏1.5 + 𝑁3 𝜏2 + 𝑁4 𝜏4 )]
𝜌𝜎 = 𝑝𝑐 ∙ 𝑒𝑥𝑝 𝑡+273.15
𝑡+273.15
with 𝜏 = 1 − ), the critical temperature 𝑡𝑐 = 45.573 °C, the critical pressure 𝑝𝑐 = 3755.0 kPa,
𝑡c +273.15
and the coefficients 𝑁1 = –7.12555484, 𝑁2 = 2.03684991, 𝑁3 = –1.55048811, 𝑁4 = –2.64100632. For
validation, the following test values are given: 𝜌𝜎 = 235.8115 kPa at 𝑡 = –49.15 °C; 𝜌𝜎 = 3740.5917 kPa
at 𝑡 = 45.40 °C. Uncertainty of these values is stated to be within better than ±0.02 % of value.
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It is important to note that that although the values of frost-point and dew-point temperatures differ,
saturation vapour pressure (and hence the humidity) is the same.
When performing measurements with a condensation hygrometer it is therefore essential to know
whether the condensate on the mirror is in the form of frost or dew.
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17.62 ∙ 𝑡
𝑒w = 611.2 ∙ exp ( ) (1)
243.12 + 𝑡
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t is the temperature in °C
22.46 ∙ 𝑡
𝑒i = 611.2 ∙ exp ( ) (2)
272.62 + 𝑡
t is the temperature in °C
𝑒
ln (
)
𝑡d = 243.12 611.2 (3)
𝑒
17.62 − ln ( )
611.2
To calculate the vapour pressure e from dew point temperature td equation 1 is used substituting the
temperature t with the dew point temperature td.
17.62 ∙ 𝑡d
𝑒 = 611.2 ∙ exp ( ) (4)
243.12 + 𝑡d
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𝑒
ln ( )
𝑡f = 272.62 611.2 (5)
𝑒
22.46 − ln ( )
611.2
To calculate the vapour pressure e from frost point temperature tf equation 2 is used substituting the
temperature t with the frost point temperature tf.
22.46 ∙ 𝑡f (6)
𝑒 = 611.2 ∙ 𝑒𝑥𝑝 ( )
272.62 + 𝑡f
𝑈w ∙ 𝑒w
𝑒= (8)
100
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𝑒
𝑈i = ∙ 100 for 𝑡 < 0 (10)
𝑒i
𝑈w,i ∙ 𝑒w,i
𝑒= (11)
100
The inverse equation for calculating the vapour pressure e from φv in µl/l and total pressure P is:
𝜑v ∙ 𝑃
𝑒= (13)
𝜑v + 106
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𝑀v 𝑒
= ∙ ∙ 106 (14)
𝑀g 𝑃 − 𝑒
Using the molecular weights for water vapour and SF6 the equation reduces to
18.02 𝑒 𝑒
𝑟= ∙ ∙ 106 = 0.123 ∙ 106 (15)
146.05 𝑃 − 𝑒 𝑃−𝑒
The inverse equation for calculating the vapour pressure e from r and total pressure p is
𝑟∙𝑃
𝑒 = 8.1 (16)
𝑟 + 106
𝑒
𝜑v = ∙ 106 (17)
𝑃
The inverse equation for calculating the vapour pressure e from µl/l and total pressure P is:
𝜑v ∙ 𝑃
𝑒= (18)
106
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𝑀v 𝑒
𝑟= ∙ ∙ 106 (19)
𝑀g 𝑃
Using the molecular weights for water vapour and SF6 the equation reduces to
18.02 𝑒 𝑒
𝑟= ∙ ∙ 106 = 0.123 ∙ 106 (20)
146.05 𝑃 𝑃
The inverse equation for calculating the vapour pressure e from r and total pressure P is
𝑟∙𝑃
𝑒 = 8.1 (21)
106
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C.2.3.1. Convert Frost Point at Pressure P1 to the equivalent Frost Point at Pressure p2.
With equation 6, use frost point temperature t1 to calculate vapour pressure e1 with respect to total
pressure P1.
22.46 ∙ 𝑡1
𝑒1 = 611.2 ∙ exp ( ) (24)
272.62 + 𝑡1
𝑃2
𝑒2 = ∙𝑒 (25)
𝑃1 1
With equation 5 and vapour pressure e2, calculate frost point temperature t2 relative to pressure P2.
𝑒2
ln ( )
𝑡2 = 272.62 611.2 (26)
𝑒
22.46 − ln ( 2 )
611.2
Example: Following this procedure, convert −20 °C frost point measured at 100 kPa absolute to the
equivalent frost point with respect to a system pressure of 450 kPa absolute.
t1= -20 °C
P1= 100 kPa absolute
P2= 450 kPa absolute
22.46 ∙ −20
𝑒1 = 611.2 ∙ exp ( ) = 103.26 (27)
272.62 + −20
450
𝑒2 = ∙ 103.26 = 464.67 (28)
100
464.67
ln ( )
𝑡2 = 272.62 611.2 = −3.3 °C (29)
464.67
22.46 − ln ( )
611.2
The frost point relative to system pressure P2 of 450 kPa absolute is −3.3 °C.
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SF6 MEASUREMENT GUIDE
µl/l ∙ 𝑃
𝑒i = (30)
µl/l + 106
With equation 5 and vapour pressure ei, calculate frost point temperature tf relative to pressure P. [Note
that if the above vapour pressure, e1, is greater than 611.2 (meaning that the result will be above 0 °C),
use the dew point formula (equation 3) instead.]
𝑒i
ln ( )
𝑡f = 272.62 611.2 (31)
𝑒
22.46 − ln ( i )
611.2
Example: Following this procedure, convert 150 ppmv to the equivalent frost point with respect to a
standard pressure Pstd of 100 kPa.
ppmv = 150
P = 100 kPa absolute = 100000 Pa absolute
150 ∙ 100000
𝑒i = = 14.998 (32)
150 + 106
14.998
ln ( )
𝑡f = 272.62 611.2 = −38.6 °C (33)
14.998
22.46 − ln ( )
611.2
The frost point relative to standard pressure P of 100 kPa absolute at 150 µl/l (ppmv) is −38.6 °C.
22.46 ∙ 𝑡f
𝑒 = 611.2 ∙ 𝑒𝑥𝑝 ( ) (34)
272.62 + 𝑡f
With equation 12, use vapour pressure e and measurement pressure P to calculate µl/l (ppmv).
𝑒
𝜑v = ∙ 106 (35)
𝑃−𝑒
Example: Following this procedure, convert a frost point of −40 °C measured at standard pressure P of
100 kPa absolute to the equivalent volume ratio in µl/l.
tf = −40 °C
P = 100 kPa = 100000 Pa
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SF6 MEASUREMENT GUIDE
22.46 ∙ −40
𝑒 = 611.2 ∙ e𝑥𝑝 ( ) = 12.850 (36)
272.62 + −40
12.850
𝜑v = ∙ 106 = 128.5 (37)
100000 − 12.850
The equivalent volume ratio to a frost point of −40 °C measured at a pressure of 100 kPa absolute is
128.5 µl/l (ppmv).
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