BS EN 60567:2011

BSI Standards Publication

Oil-filled electrical equipment —

Sampling of gases and analysis
of free and dissolved gases —
Guidance
BS EN 60567:2011 BRITISH STANDARD

National foreword
This British Standard is the UK implementation of EN 60567:2011. It is identi-
cal to IEC 60567:2011. It supersedes BS EN 60567:2005 which is withdrawn.
The UK participation in its preparation was entrusted to Technical Committee
GEL/10, Fluids for electrotechnical applications.
A list of organizations represented on this committee can be obtained on
request to its secretary.
This publication does not purport to include all the necessary provisions of a
contract. Users are responsible for its correct application.
© The British Standards Institution 2012
ISBN 978 0 580 69888 0
ICS 17.220.99; 29.035.99; 29.040.10

Compliance with a British Standard cannot confer immunity from

legal obligations.

This British Standard was published under the authority of the Standards
Policy and Strategy Committee on 29 February 2012.

Amendments issued since publication

Amd. No. Date Text affected

 BS EN 60567:2011
EUROPEAN STANDARD EN 60567
NORME EUROPÉENNE
EUROPÄISCHE NORM December 2011

ICS 29.040 Supersedes EN 60567:2005

English version

Oil-filled electrical equipment -

Sampling of gases and analysis of free and dissolved gases -
Guidance
(IEC 60567:2011)

Matériels électriques immergés - Ölgefüllte elektrische Betriebsmittel –

Echantillonnage de gaz et analyse des Probennahme von Gasen und Analyse
gaz libres et dissous - freier und gelöster Gase – Anleitung
Lignes directrices (IEC 60567:2011)
(CEI 60567:2011)

This European Standard was approved by CENELEC on 2011-11-24. CENELEC members are bound to comply
with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard
the status of a national standard without any alteration.

Up-to-date lists and bibliographical references concerning such national standards may be obtained on
application to the CEN-CENELEC Management Centre or to any CENELEC member.

This European Standard exists in three official versions (English, French, German). A version in any other
language made by translation under the responsibility of a CENELEC member into its own language and notified
to the CEN-CENELEC Management Centre has the same status as the official versions.

CENELEC members are the national electrotechnical committees of Austria, Belgium, Bulgaria, Croatia, Cyprus,
the Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy,
Latvia, Lithuania, Luxembourg, Malta, the Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia,
Spain, Sweden, Switzerland and the United Kingdom.

CENELEC
European Committee for Electrotechnical Standardization
Comité Européen de Normalisation Electrotechnique
Europäisches Komitee für Elektrotechnische Normung

Management Centre: Avenue Marnix 17, B - 1000 Brussels

© 2011 CENELEC - All rights of exploitation in any form and by any means reserved worldwide for CENELEC members.

Ref. No. EN 60567:2011 E

BS EN 60567:2011
EN 60567:2011 -2-

Foreword
The text of document 10/849/FDIS, future edition 4 of IEC 60567, prepared by IEC/TC 10 "Fluids for
electrotechnical applications" was submitted to the IEC-CENELEC parallel vote and approved by
CENELEC as EN 60567:2011.

The following dates are fixed:

• latest date by which the document has (dop) 2012-08-24

to be implemented at national level by
publication of an identical national
standard or by endorsement
• latest date by which the national (dow) 2014-11-24
standards conflicting with the
document have to be withdrawn

This document supersedes EN 60567:2005.

EN 60567:2011 includes the following significant technical changes with respect to EN 60567:2005:
Since the publication of EN 60567:2005, CIGRE TF.D1.01.15 has made progress in several areas of
dissolved gas analysis (DGA), notably

a) oil sampling,

b) laboratory analysis and solubility coefficients of gases in non-mineral oils,

c) calibration of the headspace gas extraction method,

d) more sensitive detectors for chromatography,

e) preparation of air-saturated standards and

f) evaluation of gas monitor readings.

These advances are included in EN 60567:2011.

Sampling of oil for DGA from oil-filled equipment has been moved from EN 60567 to EN 60475 as
reflected in the revised title of this standard.

Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CENELEC [and/or CEN] shall not be held responsible for identifying any or all such patent
rights.

Endorsement notice
The text of the International Standard IEC 60567:2011 was approved by CENELEC as a European
Standard without any modification.

In the official version, for Bibliography, the following notes have to be added for the standards indicated:
[1] ISO/IEC 17025 NOTE Harmonized as EN ISO/IEC 17025.

[2] ISO 3675 NOTE Harmonized as EN ISO 3675.

 BS EN 60567:2011
-3- EN 60567:2011

Annex ZA
(normative)

Normative references to international publications

with their corresponding European publications
The following referenced documents are indispensable for the application of this document. For dated
references, only the edition cited applies. For undated references, the latest edition of the referenced
document (including any amendments) applies.

NOTE When an international publication has been modified by common modifications, indicated by (mod), the relevant EN/HD
applies.

Publication Year Title EN/HD Year

IEC 60296 - Fluids for electrotechnical applications - EN 60296 -
Unused mineral insulating oils for
transformers and switchgear
IEC 60475 2011 Method of sampling insulating liquids EN 60475 2011
IEC 60599 - Mineral oil-impregnated electrical equipment EN 60599 -
in service - Guide to the interpretation of
dissolved and free gases analysis
ISO 5725 Series Accuracy (trueness and precision) of - -
measurement methods and results
ASTM D2780 - Standard Test Method for Solubility of Fixed - -
Gases in Liquids
 BS EN 60567:2011
–2– 60567 © IEC:2011

CONTENTS
INTRODUCTION ..................................................................................................................... 7
1 Scope ............................................................................................................................... 9
2 Normative references ....................................................................................................... 9
3 Sampling of gases from gas-collecting (Buchholz) relays ................................................ 10
3.1 General remarks.................................................................................................... 10
3.2 Sampling of free gases by syringe ......................................................................... 10
3.2.1 Sampling equipment .................................................................................. 10
3.2.2 Sampling procedure................................................................................... 11
3.3 Sampling of free gases by displacement of oil ....................................................... 12
3.4 Sampling of free gases by vacuum ........................................................................ 13
3.5 Sampling of oil from oil filled equipment ................................................................ 14
4 Labelling of gas samples ................................................................................................ 14
5 Sampling, labelling and transferring of oil from oil-filled equipment ................................. 14
5.1 Sampling and labelling of oil .................................................................................. 14
5.2 Transfer of oil for DGA analysis ............................................................................. 14
5.2.1 Transfer from oil syringes .......................................................................... 14
5.2.2 Transfer from ampoules ............................................................................. 15
5.2.3 Transfer from flexible metal bottles ............................................................ 15
5.2.4 Transfer from glass and rigid metal bottles ................................................ 15
6 Preparation of gas-in-oil standards ................................................................................. 15
6.1 General remark ..................................................................................................... 15
6.2 First method: preparation of a large volume of gas-in-oil standard ......................... 15
6.2.1 Equipment ................................................................................................. 15
6.2.2 Procedure .................................................................................................. 16
6.2.3 Calculation ................................................................................................ 18
6.3 Second method: preparation of gas-in-oil standards in a syringe or a vial .............. 18
6.3.1 Equipment ................................................................................................. 19
6.3.2 Procedure .................................................................................................. 20
7 Extraction of gases from oil ............................................................................................ 20
7.1 General remarks.................................................................................................... 20
7.2 Multi-cycle vacuum extraction using Toepler pump apparatus ............................... 21
7.2.1 Toepler pump extraction apparatus ............................................................ 21
7.2.2 Extraction procedure ................................................................................. 24
7.3 Vacuum extraction by partial degassing method .................................................... 25
7.3.1 General remark ......................................................................................... 25
7.3.2 Partial degassing apparatus ...................................................................... 25
7.3.3 Extraction procedure ................................................................................. 26
7.4 Stripping extraction method ................................................................................... 26
7.4.1 Stripping apparatus ................................................................................... 26
7.4.2 Outline of procedure .................................................................................. 29
7.5 Headspace method ............................................................................................... 30
7.5.1 Principle of the method .............................................................................. 30
7.5.2 Symbols and abbreviations ........................................................................ 30
7.5.3 Headspace extraction apparatus................................................................ 31
7.5.4 Headspace extraction procedure ............................................................... 35
BS EN 60567:2011
60567 © IEC:2011 –3–

7.5.5 Calibration of the headspace extractor ...................................................... 39

8 Gas analysis by gas-solid chromatography ..................................................................... 41
8.1 General remarks.................................................................................................... 41
8.2 Outline of suitable methods using Table 4 ............................................................. 42
8.3 Apparatus .............................................................................................................. 42
8.3.1 Gas chromatograph ................................................................................... 42
8.3.2 Columns .................................................................................................... 44
8.3.3 Carrier gas ................................................................................................ 44
8.3.4 Detectors ................................................................................................... 44
8.3.5 Methanator ................................................................................................ 44
8.3.6 Cold trap ................................................................................................... 44
8.3.7 Integrator and recorder .............................................................................. 44
8.4 Preparation of apparatus ....................................................................................... 45
8.5 Analysis ................................................................................................................ 45
8.6 Calibration of the chromatograph ........................................................................... 45
8.7 Calculations .......................................................................................................... 46
9 Quality control ................................................................................................................ 46
9.1
Verification of the entire analytical system ............................................................. 46
9.2
Limits of detection and quantification ..................................................................... 47
9.3
Repeatability, reproducibility and accuracy ............................................................ 47
9.3.1 General remark ......................................................................................... 47
9.3.2 Repeatability ............................................................................................. 48
9.3.3 Reproducibility ........................................................................................... 48
9.3.4 Accuracy ................................................................................................... 48
10 Report of results ............................................................................................................. 49
Annex A (informative) Correction for incomplete gas extraction in partial degassing
method by calculation ........................................................................................................... 51
Annex B (informative) Mercury-free and shake test versions of the standard extraction
methods ................................................................................................................................ 53
Annex C (informative) Preparation of air-saturated standards .............................................. 55
Annex D (informative) Correction for gas bubbles in syringes and air gap in rigid
bottles .................................................................................................................................. 56
Annex E (informative) Procedure for comparing gas monitor readings to laboratory
results .................................................................................................................................. 57
Bibliography .......................................................................................................................... 58

Figure 1 – Sampling of gas by syringe .................................................................................. 11

Figure 2 – Sampling of free gases by oil displacement .......................................................... 12
Figure 3 – Sampling of free gases by vacuum ....................................................................... 13
Figure 4 – First method of preparing gas-in-oil standards ..................................................... 17
Figure 5 – Second method for preparing gas-in-oil standards ................................................ 19
Figure 6 – Example of a Toepler pump extraction apparatus ................................................. 23
Figure 7 – Types of glass strippers ....................................................................................... 27
Figure 8 – Stainless steel stripper ......................................................................................... 28
Figure 9 – Schematic arrangement for connecting an oil stripper to a gas
chromatograph ...................................................................................................................... 29
Figure 10 – Schematic representation of headspace sampler ................................................ 30
 BS EN 60567:2011
–4– 60567 © IEC:2011

Figure 11 – Vial filled with water ........................................................................................... 32

Figure 12 – Revolving table .................................................................................................. 34
Figure 13 – Schematic arrangement for gas chromatography ................................................ 43
Figure B.1 – Schematic representation of methods in Annex B ............................................. 54

Table 1 – Information required for gas samples .................................................................... 14

Table 2 – Examples of headspace operating conditions ........................................................ 35
Table 3 – Headspace partition coefficients at 70 °C in mineral insulating oil ......................... 40
Table 4 – Examples of gas chromatographic operating conditions ......................................... 41
Table 5 – Required limits of detection in oil ........................................................................... 47
Table 6 – Examples of accuracy of extraction methods ......................................................... 49
Table A.1 – Examples of solubility coefficients a i (at 25 ºC) reported by CIGRE TF
D1.01.15 ............................................................................................................................... 51
Table C.1 – Examples of solubility values of air for different oil types ................................... 55
Table C.2 – Examples of temperature variations for oxygen and nitrogen solubility in
mineral oil ............................................................................................................................. 55
BS EN 60567:2011
60567 © IEC:2011 –7–

INTRODUCTION

Gases may be formed in oil-filled electrical equipment due to natural ageing but also, to a
much greater extent, as a result of faults.

Operation with a fault may seriously damage the equipment, and it is valuable to be able to
detect the fault at an early stage of development.

Where a fault is not severe, the gases formed will normally dissolve in the oil, with a small
proportion eventually diffusing from the liquid into any gas phase above it. Extracting
dissolved gas from a sample of the oil and determining the amount and composition of this
gas is a means of detecting such faults, and the type and severity of any fault may often be
inferred from the composition of the gas and the rate at which it is formed.

In the case of a sufficiently severe fault, free gas will pass through the oil and collect in the
gas-collecting (Buchholz) relay if fitted; if necessary, this gas may be analysed to assist in
determining the type of fault that has generated it. The composition of gases within the
bubbles changes as they move through the oil towards the gas-collecting relay.

This can be put to good use, as information on the rate of gas production may often be
inferred by comparing the composition of the free gases collected with the concentrations
remaining dissolved in the liquid.

The interpretation of the gas analyses is the subject of IEC 60599.

These techniques are valuable at all stages in the life of oil-filled equipment. During
acceptance tests on transformers in the factory, comparison of gas-in-oil analyses before,
during and after a heat run test can show if any hot-spots are present, and similarly analysis
after dielectric testing can add to information regarding the presence of partial discharges or
sparking. During operation in the field, the periodic removal of an oil sample and analysis of
the gas content serve to monitor the condition of transformers and other oil-filled equipment.

The importance of these techniques has led to the preparation of this standard, to the
procedures to be used for the sampling, from oil-filled electrical equipment, of gases and oils
containing gases, and for subsequent analysis.

NOTE Methods described in this standard apply to insulating oils, since experience to date has been almost
entirely with such oils. The methods may also be applied to other insulating liquids, in some cases with
modifications.

General caution, health, safety and environmental protection

This International Standard does not purport to address all the safety problems associated
with its use. It is the responsibility of the user of the standard to establish appropriate health
and safety practices and determine the applicability of regulatory limitations prior to use.

The insulating oils which are the subject of this standard should be handled with due regard to
personal hygiene. Direct contact with the eyes may cause irritation. In the case of eye
contact, irrigation with copious quantities of clean running water should be carried out and
medical advice sought. Some of the tests specified in this standard involve the use of
processes that could lead to a hazardous situation. Attention is drawn to the relevant standard
for guidance.

Mercury presents an environmental and health hazard. Any spillage should immediately be
removed and be properly disposed of. Consult local regulations for mercury use and handling.
Mercury-free methods may be requested in some countries.
 BS EN 60567:2011
–8– 60567 © IEC:2011

Environment

This standard is applicable to insulating oils, chemicals and used sample containers.

Attention is drawn to the fact that, at the time of writing of this standard, many insulating oils
in service are known to be contaminated to some degree by PCBs. If this is the case, safety
countermeasures should be taken to avoid risks to workers, the public and the environment
during the life of the equipment, by strictly controlling spills and emissions. Disposal or
decontamination of these oils should be carried out strictly according to local regulations.
Every precaution should be taken to prevent release of insulating oil into the environment.
BS EN 60567:2011
60567 © IEC:2011 –9–

OIL-FILLED ELECTRICAL EQUIPMENT –

SAMPLING OF GASES AND ANALYSIS
OF FREE AND DISSOLVED GASES –
GUIDANCE

1 Scope

This International Standard deals with the techniques for sampling free gases from gas-
collecting relays from power transformers. Three methods of sampling free gases are
described.

The techniques for sampling oil from oil-filled equipment such as power and instrument
transformers, reactors, bushings, oil-filled cables and oil-filled tank-type capacitors are no
longer covered by this standard, but are instead described in 4.2 of IEC 60475:2011.

Before analysing the gases dissolved in oil, they are first extracted from the oil. Three basic
methods are described, one using extraction by vacuum (Toepler and partial degassing),
another by displacement of the dissolved gases by bubbling the carrier gas through the oil
sample (stripping) and the last one by partition of gases between the oil sample and a small
volume of the carrier gas (headspace). The gases are analysed quantitatively after extraction
by gas chromatography; a method of analysis is described. Free gases from gas-collecting
relays are analysed without preliminary treatment.

The preferred method for assuring the performance of the gas extraction and analysis
equipment, considered together as a single system, is to degas samples of oil prepared in the
laboratory and containing known concentrations of gases (“gas-in-oil standards”) and
quantitatively analyse the gases extracted. Two methods of preparing gas-in-oil standards are
described.

For daily calibration checks of the chromatograph, it is convenient to use a standard gas
mixture containing a suitable known amount of each of the gas components to be in a similar
ratio to the common ratios of the gases extracted from transformer oils .

The techniques described take account, on the one hand, of the problems peculiar to
analyses associated with acceptance testing in the factory, where gas contents of oil are
generally very low and, on the other hand, of the problems imposed by monitoring equipment
in the field, where transport of samples may be by un-pressurized air freight and where
considerable differences in ambient temperature may exist between the plant and the
examining laboratory.

2 Normative references

The following documents, in whole or in part, are normatively referenced in this document and
are indispensable for its application. For dated references, only the edition cited applies. For
undated references, the latest edition of the referenced document (including any
amendments) applies.

IEC 60296, Fluids for electrotechnical applications – Unused mineral insulating oils for
transformers and switchgear

IEC 60475:2011, Method of sampling insulating liquids

 BS EN 60567:2011
– 10 – 60567 © IEC:2011

IEC 60599, Mineral oil-impregnated electrical equipment in service – Guide to the inter-
pretation of dissolved and free gases analysis

ISO 5725 (all parts), Accuracy (trueness and precision) of measurement methods and results

ASTM D2780, Standard Test Method for Solubility of Fixed Gases in Liquids

3 Sampling of gases from gas-collecting (Buchholz) relays

3.1 General remarks

It is important to bear in mind that receiving a qualitative and a representative sample is

crucial for obtaining a reliable diagnosis of the electrical equipment. Even the most
sophisticated extraction or diagnosis methods cannot overcome faulty samples.

Gas samples from relays should be taken from the equipment with the minimum delay after
gas accumulation has been signalled. Changes in composition caused by the selective re-
absorption of components may occur if free gases are left in contact with oil.

Certain precautions are necessary when taking gas samples. The connection between the
sampling device and the sampling vessel shall avoid the ingress of air. Temporary
connections should be as short as possible. Any rubber or plastic tubing used should have
been proved to be impermeable to gases.

Gas samples should be properly labelled (see Clause 4) and analysed without undue delay to
minimize hydrogen loss (for example, within a maximum period of one week).

Oxygen, if present in the gas, may react with any oil drawn out with the sample. Reaction is
delayed by excluding light from the sample, for example, by wrapping the vessel in aluminium
foil or suitable opaque material.

Of the three methods described below, the syringe method is recommended. The other two
methods are alternatives to be used exclusively in case of serious hindrance.

Sampling into a sampling tube by liquid displacement using transformer oil as a sealing liquid
is simple, but the different solubilities of the gas components may need to be taken into
account if the gas quantity is such that some oil remains in the tube.

The vacuum method requires skill to avoid contaminating the sample by leakage of air into the
system. It is particularly true where the gas to be sampled may be at less than atmospheric
pressure (for example, some sealed transformers).

3.2 Sampling of free gases by syringe

3.2.1 Sampling equipment

NOTE Figures in brackets refer to those circled numbers in the relevant figure.

See Figure 1. The equipment shall be as follows:

a) Impermeable oil-resistant plastic or rubber tubing (3) provided with a connecter to fit onto
a suitable sampling connection of the gas-collecting relay. To avoid cross-contamination,
the tubing should be used only once.
b) Gas-tight syringes of suitable volume (1) (25 ml to 250 ml). Medical or veterinary quality
glass syringes with ground-in plungers may be suitable; alternatively, syringes with oil-
proof seals may be used. The syringe should be fitted with a cock enabling it to be sealed.
It is often convenient to use the same syringes for both gas sampling and for oil sampling
(see 4.2.2 of IEC 60475:2011).
BS EN 60567:2011
60567 © IEC:2011 – 11 –

The gas tightness of a syringe may be tested by storing an oil sample containing a
measurable quantity of hydrogen for at least two weeks and analysing aliquots for
hydrogen at the beginning and end of the period. An acceptable syringe will permit losses
of hydrogen of less than 2,5 % per week. General experience suggests that all-glass
syringes leak less than those using plastic seals. Improvement of the gas tightness may
be obtained by the use of a lubricant such as a light grease or transformer oil.
It is a good practice to test the integrity of syringes and valve system before the sampling.
A recommended procedure appears in Annex B of IEC 60475:2011.
c) Transport containers should be designed to hold the syringe firmly in place during
transport, but allow the syringe plunger freedom to move, and prevent its tip from
contacting the container, whatever its position during transportation.

Position
5 4
of valve

2 1
3

6 4

IEC 2457/11

Key
1 syringe 5 equipment sampling valve
2 stopcock 6 gas-collecting relay valve
3 rubber connecting tubing 7 waste vessel
4 three-way valve

Figure 1 – Sampling of gas by syringe

3.2.2 Sampling procedure

The apparatus is connected as shown in Figure 1. The connections should be as short as

possible and filled with oil at the start of sampling.

The sampling valve (5) is opened. If sampling from a gas-collecting relay on a transformer
fitted with a conservator, a positive pressure will exist; the three-way valve (4) is carefully
turned to position A and the oil in the connecting tubing (3) allowed to flow to waste (7). When
gas reaches the three-way valve (4), the latter is turned to position B to connect the pre-
lubricated syringe (1). The stopcock (2) is then opened and the syringe allowed to fill under
the hydrostatic pressure, taking care that its plunger is not expelled. When a sufficient sample
 BS EN 60567:2011
– 12 – 60567 © IEC:2011

has been taken, the stopcock (2) and sampling valve (5) are closed and the apparatus is
disconnected.

The oil in the syringe is expelled by inverting the syringe and applying gentle pressure to the
plunger.

Label carefully the sample (see Clause 4).

3.3 Sampling of free gases by displacement of oil

This method is reliable only where the gas sample is at or above atmospheric pressure. The
apparatus is shown in Figure 2.

The sampling tube (5), typically of 100 ml capacity, is preferably of glass since the operator
can then see how much oil remains in it during gas sampling. The sampling tube is filled with
oil from the transformer on site. Before being used as described below, the connecting tube
(3) should also be filled with oil.

The open end of the connecting tube (3) is fitted onto the gas-sampling valve (2). The
sampling valve and inlet stopcock of the sampling tube are opened. The sampling tube is
inclined so that its closed end is the lowest point. The outlet stopcock on the sampling tube is
then opened, allowing oil to run out to waste (6), drawing first any oil from the connection
between relay and sampling valve, and the gas from the relay, into the sampling tube.

Sampling is complete when the gas-collecting relay is completely filled with oil or when nearly
all oil has gone from the sampling tube.

Both stopcocks (4) on the sampling tube and the sampling valve (2) are closed and then the
connections removed.

2
3

5
1

IEC 2458/11

Key
1 gas collecting relay valve 4 stopcock
2 equipment sampling valve 5 sampling tube
3 oil-resistant connecting tubing 6 waste vessel

Figure 2 – Sampling of free gases by oil displacement

BS EN 60567:2011
60567 © IEC:2011 – 13 –

3.4 Sampling of free gases by vacuum

The apparatus is connected as shown in Figure 3. With the equipment sampling valve closed,
stopcocks (1), (2) and (10) open, and the three-way valve (4) turned to position A, the vacuum
pump (12) is allowed to evacuate the connecting tubing, the trap and the sampling vessel.

A satisfactory vacuum will be below 100 Pa. The system should be checked for leaks by
closing the pump suction stopcock (10) and observing that no appreciable change in vacuum
occurs. Over a time equal to that which will be taken for sampling, the pressure should not
increase by more than 100 Pa. Similarly, the stopcock (1) on the sampling tube should be
vacuum tight to the same degree over several weeks.

If the connecting tubing between the equipment sampling valve (5) and the gas-collecting
relay is filled with oil, the three-way valve (4) is turned to position (B). The equipment
sampling valve (5) is carefully opened and oil allowed to flow into the trap (9). When the end
of the oil stream is observed to reach the three-way valve (4), it is turned to position D to
evacuate the oil from it. Thereafter, valve (4) is turned to position C. When sampling is
complete, stopcock (1) is closed first, then the equipment sampling valve (5) closed and the
apparatus disconnected.

If the connecting tubing between the equipment and the sampling valve is empty of oil, the
procedure for draining oil is omitted and the three-way valve (4) used in position C after
evacuating and testing that the apparatus is leak tight.

B
5 3 Position
4
of valve
C

3 1 28
3 3
8

4
9

12 10
IEC 2459/11

Key
1 vacuum tight stopcock 8 vacuum gauge
2 vacuum tight stopcock 9 trap
3 rubber connecting tubing 10 vacuum tight stopcock
4 vacuum tight three-way valve 12 vacuum pump
5 equipment sampling valve 28 sampling tube
6 gas collecting relay valve

Figure 3 – Sampling of free gases by vacuum

 BS EN 60567:2011
– 14 – 60567 © IEC:2011

3.5 Sampling of oil from oil filled equipment

See 4.2 to 4.4 of IEC 60475:2011.

4 Labelling of gas samples

Gas samples should be properly labelled before dispatch to the laboratory.

The following information, as shown in Table 1, is necessary (whenever it is known).

Table 1 – Information required for gas samples

Transformer Sampling
Customer Sampling date and time following a gas alarm
Location Sampling point
Identification number Sampling person
Manufacturer Reason for analysis
General type (power, instrument or Transformer non-energized, off-load energized
industrial) or on-load
Rated MVA
Voltage ratio
Type and location of OLTC
Date of commissioning
Oil
Type of oil (mineral or non-mineral) Weight (or volume) of oil
Product name Date of last oil treatment

The following additional information is desirable:

– ambient temperature, reading of MVA or load current or percentage load, operation of

pumps, mode of communication of its tap-changer with the main tank, oil preservation
system (conservator, nitrogen blanket, etc.), and any changes in operational conditions or
any maintenance carried out since last sampling;
– time of sampling where more than one sample is taken.

5 Sampling, labelling and transferring of oil from oil-filled equipment

5.1 Sampling and labelling of oil

Consult 4.2 to 4.4 of IEC 60475:2011 for sampling equipment, sampling procedures and
labelling to be used.

5.2 Transfer of oil for DGA analysis

5.2.1 General

For transferring oil from its sample container into the gas extraction vessels of Article 7, the
following procedures should be used:

5.2.2 Transfer from oil syringes

Introduce a portion of the oil sample in the syringe into the gas extraction vessel by turning
the three-way valve of the syringe to position B of Figure 5 of IEC 60475:2011.
BS EN 60567:2011
60567 © IEC:2011 – 15 –

5.2.3 Transfer from ampoules

Attach the ampoule in the vertical position. Install a three-way plastic valve between the
bottom plastic tubing of the ampoule and another piece of plastic tubing going to a waste oil
container. Attach a glass syringe to the three-way plastic valve. Open the upper cock then the
lower cock of the ampoule. Fill the syringe with oil following procedures indicated in 4.2.2.2 of
IEC 60475:2011. Transfer a portion of the oil sample in the syringe into the gas extraction
vessel as indicated in 5.2.2 above.

5.2.4 Transfer from flexible metal bottles

Open the screw cap of the bottle, introduce a long needle down to the bottom of the bottle,
attach a glass syringe with a three-way valve to the needle and gently (to avoid creating gas
bubbles due to negative pressure) draw a sample of oil into the syringe. Detach the three-way
valve from the needle and invert the syringe to expel any gas bubble introduced in the oil.
Then introduce a portion of the oil sample in the syringe into the gas extraction chamber as
indicated in 5.2.2 above. Alternatively, a piece of tubing can be used to draw oil directly into
the gas extraction vessel (Toepler or partial degassing) under vacuum.

The first sample taken from the bottle should always be used for DGA analysis. No other
sample should be taken for DGA analysis, since significant gas loss may occur into the
headspace of the bottle.

5.2.5 Transfer from glass and rigid metal bottles

The procedure used for flexible metal bottles in 5.2.4 is suitable for glass and rigid metal
bottles.

6 Preparation of gas-in-oil standards

6.1 General remark

As noted in Clause 1, the preferred method of assuring the performance of the entire system
for gas extraction and analysis is to analyse oils containing known concentrations of gases
(gas-in-oil standards).

Two methods of preparing gas-in-oil standards are described below, a general method and a
simpler method. The first method has the benefit of producing much larger quantities of oil.

NOTE If gas-in-oil standards are commercially available they can be used, provided they fulfil quality assurance
requirements.

6.2 First method: preparation of a large volume of gas-in-oil standard

6.2.1 Equipment

A suitable apparatus design consists of (see Figures 4a, 4b, 4c):

– a magnetic stirrer (12);

– a 5 l oil vessel (13) equipped with three side-arm outlets, two of which are fitted with high-
vacuum stopcocks (1) and (2) and one with a rubber septum (16);
– a 6 l reservoir (14) equipped with a high-vacuum stopcock (3) connected with a 75 ml
splash bulb (15) and a high-vacuum stopcock (4);
– a mercury displacement system (17) consisting of two 500 ml mercury glass bulbs
connected with a high-vacuum oil-resistant flexible rubber tubing.

The gas-injection system (Figures 4e to 4g) consists of

– a set of gas tight syringes of appropriate volumes (18),

 BS EN 60567:2011
– 16 – 60567 © IEC:2011

– a plastic three-way valve of standard type (7), modified to minimize dead volume by
inserting pieces of stainless steel tubing (approximately 0,4 mm inner diameter (ID) and
1,5 mm outer diameter (OD)) into the inner branches and connected to a gas-injecting
needle (10) (approximately 10 cm long, 0,25 mm OD) to go through the rubber septum into
the oil flask (16),
– gas cylinders equipped with a pressure reducer and a valve (20),
NOTE 1 Gas cylinders containing each of the individual gases to be injected can be used. Ready-made
mixtures of these gases can also be obtained from some gas suppliers.

– a length of oil-resistant flexible tubing connecting the gas cylinder to the three-way valve
(7) and incorporating a hypodermic needle (approximately 0,3 mm ID and 0,6 mm OD).
The latter acts as a leak to a water bubbler (21) which is used to check the absence of
back diffusion.
NOTE 2 Replace the length of tubing connecting the gas cylinder to the three-way valve after each gas
change.

The oil sampling system (Figures 4h to 4k) consists of glass syringes (19) of suitable capacity
equipped with two three-way plastic valves (8)) and (9) and an oil-extracting needle (11)
(approximately 0,6 mm ID, 1,0 mm OD and 120 mm long).

6.2.2 Procedure
NOTE Figures in brackets refer to those circled numbers in Figures 4a to 4k. The positions A to D of the three-
way valves (7, 8 and 9) are illustrated in Figure 4d.

6.2.2.1 Degassing the oil

a) Thoroughly clean all the glassware before assembling.

b) Secure the rubber septum and the flexible connections with pieces of twisted metal wire.
c) Clean, if necessary, approximately 1 l of mercury with pentane and filter through a finely
pierced filter paper.
d) Adapt the oil reservoir (14), the splash bulb (15) and stopcocks (4) to the 5 l vessel (13).
Connect the system to the vacuum pump (V) and evacuate the splash bulb (15) and the
5 l oil vessel (13) by opening stopcocks (2) and (4).
e) Fill the oil reservoir (14) with mineral insulating oil complying with IEC 60296 and allow oil
to flow slowly through stopcock (3) into the 5 l vessel (13) until it is full. Then close the
stopcock (2) and remove the oil reservoir (14) and the splash bulb.
NOTE If the procedure is followed carefully (filling time about 4 h) the oil in the vessel will be virtually gas-free.

f) Turn the oil vessel to bring it into the position shown in Figure 4c. Place a wet cloth over it
to prevent its temperature rising and attach the mercury displacement system (17) to
stopcock (1). Introduce 750 ml of mercury into the system with stopcock (6) closed.
g) Connect the system to the vacuum (V), open the stopcock (5) and evacuate the section
between stopcocks (1) and (6). Open the stopcock (6) to allow mercury to rise up to
stopcocks (1) and (5), and then close stopcock (5). Raise the left bulb of the system (see
Figure 7c) so that the mercury level is above the oil flask. Open the stopcock (1). Remove
the wet cloth and switch on the magnetic stirrer (12).
BS EN 60567:2011
60567 © IEC:2011 – 17 –

4
16

15 14 1
Oil 2
16 V
13 2
3
5
12
2 13 17
1 6
1
12 12
a) b) c)

18
A

Position B
of valves

7 8 9 C

20
21
D
7

d) 10

e) f) g)
19

6
B B
B B
9

11

h) i) j) k)

IEC 2460/11

Key
1 vacuum stopcocks 9 three-way valves 17 mercury displacement system
2 vacuum stopcocks 10 gas-injecting needle 18 precision gas-tight syringe
3 vacuum stopcocks 11 oil-sampling needle 19 glass syringe
4 vacuum stopcocks 12 magnetic stirrer 20 gas cylinder with pressure reducer
5 vacuum stopcocks 13 5 l oil vessel and valve
6 vacuum stopcocks 14 6 l oil vessel 21 leak to water bubbler
7 three-way valves 15 75 ml splash bubble V connection to vacuum pump
8 three-way valves 16 rubber septum
Figure 4 – First method of preparing gas-in-oil standards
 BS EN 60567:2011
– 18 – 60567 © IEC:2011

6.2.2.2 Preparation of gas-in-oil standards

See Figures 4c to 4g.

a) To inject the gases, attach the modified three-way valve (7), in position B, to the gas-
injecting needle (10). Then push the needle through the rubber septum (16) into the oil.
Turn the three-way valve to position D to purge the needle and valve with oil, then turn it
to position B. Attach to valve (7) the barrel of a precision calibrated gas-tight syringe (18)
of appropriate volume (precision within 1 %) and the gas cylinder connecting tubing (see
Figure 4e). Allow a gentle flow of gas to flush the barrel, then slowly push the plunger
several times into the barrel, finally down to the volume of gas to be injected, making sure
there is continuous bubbling through the needle leak (21).
b) Switch valve (7) to the injection position A, lower the mercury level below the needle tip,
and push the plunger to inject the gas volume into the oil. Switch valve (7) to position B
and raise the left mercury bulb above the oil vessel.
c) Repeat the same procedure with each of the gases to be dissolved then remove the gas
needle and valve (7).
When all the gases are dissolved, switch off the magnetic stirrer. Record the atmospheric
pressure and temperature.
NOTE Instead of adding individual gases, it is more convenient to use a standard gas mixture, preferably
containing all the gases listed in 8.1, in proportions representative of those found in the sampled oil.

6.2.2.3 Sampling of gas-in-oil standards

See Figures 4h to 4k.

a) To remove oil samples from the 5 l vessel (13), attach two three-way valves (8) and (9)
turned in position B, according to Figure 4b, to the liquid-withdrawing needle (11) and
push the needle through the rubber septum (16). With the mercury level up, switch valves
(8) and (9) to the draw-off position D to purge them with oil (see Figure 4i).
b) Attach a syringe (19) and turn both valves (8) and (9) to position A, and draw out a
suitable volume of oil (see Figure 4j). Then turn valve (8) to position C and valve (9) to
position B and remove the syringe together with valve (8) (see Figure 4k).

To remove more oil, additional mercury shall be added to the mercury displacement system.

6.2.3 Calculation

Calculate the concentration of each gas “i” dissolved as follows:

Ci = Vi V × 10 6

where
C i is the concentration of gas “i”, in µl/l;
V i is the volume of gas “i” injected, corrected to 20 °C and 101,3 kPa in ml;
V is the exact volume of oil in the 5 l oil flask, in ml.

6.3 Second method: preparation of gas-in-oil standards in a syringe or a vial

See Figures 5a to 5f.

BS EN 60567:2011
60567 © IEC:2011 – 19 –

4 2

a)
22
20
21

3 1

A
b)

Position
3 B 3 1
of valve 2 4

C c)

3 1

d)

3 1

e)

1
3

Oil f)

Air

IEC 2461/11

Key
1 glass syringe 20 gas bottle fitted with a pressure reducer and a valve
2 precision gas-tight syringe 21 leak to water bubbler
3 three-way valve 22 silicone rubber tubing
4 gas-injecting needle

Figure 5 – Second method for preparing gas-in-oil standards

6.3.1 Equipment

Equipment consists of

– a set of gas-tight syringes of appropriate volume (2),

 BS EN 60567:2011
– 20 – 60567 © IEC:2011

– a set of glass syringes of appropriate volume (1),

– a set of gas-injecting needles (4),
– three-way plastic valves (3),
– gas cylinders equipped with a pressure reducer and a valve (20).
NOTE Gas cylinders containing each of the individual gases to be injected may be used. Ready-made mixtures of
these gases can also be obtained from some gas suppliers.

6.3.2 Procedure

a) Bubble argon through 1 l of oil for 1 h under agitation, adjusting gas flow to maintain
agitation of the oil in order to purge all the other dissolved gases. Degas this argon-
saturated oil under a vacuum down to 1 Pa over an 8 µm-filter, in a 2 l vessel (residual
contents of 500 µl/l O 2 and 2 000 µl/l N 2 are acceptable). When the oil is completely
degassed, break the vacuum with argon up to 20 kPa.
b) Weigh a 100 ml glass syringe containing 10 ml of glass beads. Connect the syringe to the
bottom of the 2 l vessel and purge the syringe twice with 20 ml of oil. Make sure the
cylinder and plunger are completely wetted with oil. Fill the syringe with 90 ml of degassed
oil.
c) Connect a gas-tight syringe of the required volume with a needle long enough to introduce
a gas mixture in the syringe cylinder part, for instance of 115 mm length, to a cylinder
containing a standard gas mixture, and purge 4 times with the standard gas. Fill the
syringe with a known volume of standard gas. Insert the needle through the tip of the oil
syringe and transfer the volume of standard gas into the oil syringe. Reweigh to determine
the actual oil volume. Wrap the oil syringe with aluminium foil to avoid degradation with
daylight and attach it to a laboratory 3-D shaker. Shake for 1 h or until all gasses are
dissolved.
NOTE 1 Any other procedure that assists dissolution of gases in oil (for example, mixing with magnetic
stirrer or other) is suitable and can be used.

d) Record the atmospheric pressure and temperature: also refer to the note in 6.2.2.2.
Calculate the dissolved gas concentration from oil volume, injected calibration gas
volume, temperature and atmospheric pressure, as in 6.2.3. Express the quantities of
gases injected in µmoles, or in µl converted to normal conditions (20 ºC; 101,3 kPa).
e) Repeat the procedure in order to obtain at least 3 gas-in-oil samples (in the case of
headspace only) having concentrations that allow a calibration curve to be drawn covering
the values expected in the unknown samples.
NOTE 2 If a total gas-saturated mixture is desired, draw dry CO 2 -free air or nitrogen into the syringe to make,
with the gases already injected, a total of 10 % to 8 % of the oil volume according to the gas chosen (see
Figure 5f).

Turn the three-way valve (3) to position A and shake the syringe again until the air or
nitrogen is dissolved. Cooling the syringe in a refrigerator accelerates the dissolution of
the gas in the oil.
NOTE 3 A vial may be used instead of a syringe. Fill the vial with the same amount of degassed oil as that
needed when the ordinary analysis is performed, with the exact volume of oil measured by weight. Introduce
into this vial known quantities of a calibrated gas mixture, so that the concentrations in the oil are in the same
range as in the unknown field sample.

7 Extraction of gases from oil

7.1 General remarks

Removal of dissolved gases from oil for analysis may be accomplished either by vacuum
extraction, stripping or headspace.

The multi-cycle vacuum extraction (Toepler) method is described in 7.2.

The single-cycle vacuum extraction (partial degassing) method is described in 7.3.

BS EN 60567:2011
60567 © IEC:2011 – 21 –

The stripping method is described in 7.4.

The headspace method is described in 7.5.

7.2 Multi-cycle vacuum extraction using Toepler pump apparatus

7.2.1 General

In this method, an operating procedure which attempts to remove as much as possible of the
dissolved gas from the oil is used. It is normally possible to remove about 97 % of the more
soluble gases and even higher percentages of the less soluble gases. Such a small
imperfection is rarely significant when considering overall accuracies, but, in any case, the
preferred method of calibration using gas-in-oil standards takes account of incomplete
extraction.

NOTE To calibrate this method with gas-in-oil standards, the procedure described in 6.2 for preparation of argon-
free standards should be used, since the calculation will be affected by the amount of dissolved argon that will be
extracted but not detected by the gas chromatograph.

7.2.2 Toepler pump extraction apparatus

An example of a suitable design is shown in Figure 6a. Note that Figure 6b includes
recommended volumes. In this design, oil containing gas in solution is injected through a
septum (9). Alternatively, after the equipment has been evacuated, oil may be withdrawn from
an oil sample bottle via a tube attached to valve (V8) that has previously been filled with oil
(see Figure 6c).

The Toepler pump extraction apparatus shall

a) be capable of subjecting the liquid to a vacuum less than 10 Pa,

b) be vacuum-tight. The vacuum tightness of the whole system may be verified by carrying
out the extraction procedure but without introducing oil, as follows:
carry out steps b), c) and d) of 7.2.3. Omit step e). Continue with steps f), g) and h) as if
oil were present. After compression of gas to atmospheric pressure in step h), the amount
of gas should be less than 0,1 ml,
c) permit the measurement of extracted gas to be made to the nearest 0,05 ml or better, at
normal temperature and pressure.

In addition:

d) all tubing connecting the degassing flask (3) to the gas collection flask (2) (in Figure 6a)
shall be of large bore, at least 5 mm internal diameter and as short as practicable;
e) the vacuum gauge used cannot be of a type that operates at high temperature or uses
ionizing radiation (thermocouple, ionization or Penning gauges) since these can produce
gases of the types being measured by cracking the oil vapours present in the system.
Since it may react with extracted gases, a Pirani gauge is not suitable either. A sensor
based on capacitance changes between two chambers is suitable. It is recommended that
two sensors be used, one in the vacuum chamber, the second for measuring gas volumes
at atmospheric pressure.

Further requirements are noted in 7.3 in which the partial degassing method is described.

Since the detailed design of this apparatus is not standardized, it is necessary to establish an
operation that will ensure adequate extraction of all components of the dissolved gas. The
main parameters that need to be established are the number of degassing cycles (strokes) of
the Toepler pump that should be used and the time for which each degassing cycle should
last. This operation is preferably established by degassing a gas-in-oil standard as follows.
 BS EN 60567:2011
– 22 – 60567 © IEC:2011

Use the extraction procedure as detailed in 7.2.3 but, instead of degassing an unknown oil
sample, substitute a gas-in-oil standard of the volume normally used containing all the gases
listed in 8.1.

Degas successive standards until a number of cycles of the Toepler pump, together with a
degassing time on each stroke, has been established so that the area or height of each peak
on the chromatogram of the extracted gases is within 95 % of the area or height of that peak
on the chromatogram of the same quantities of gases injected directly into the chromatograph
by means of a standard gas mixture (see 8.6).

A degassing time on each cycle of 1 min to 3 min for mineral oils is frequently used; the
shorter the time the more degassing cycles are likely to be required. Similar degassing times
can be used for non-mineral oils of similar viscosity, and longer ones for more viscous oils
(e.g., 5 min to 10 min for silicone oils).

The above procedure serves to establish a routine of operation, which will apply until any
major changes are made to the equipment and will also apply to other equipment of the same
design. It is recommended that the overall calibration of the complete equipment (degassing
equipment plus chromatograph) is checked periodically (for example, every six months) using
gas-in-oil standards to provide correction factors to be applied to areas or heights of
chromatogram peaks.
BS EN 60567:2011
60567 © IEC:2011 – 23 –

C
SL
V1 V3
4

CG 5 B a

6
V2
9

11 2
3

4 A
VP2 b
c
8 d
V5
5 V12
a 1
9 V4
V7 V10
Figure 6b – Recommended volumes of
V8 several parts of a Toepler pump
2

V11
3 V9 V6 VP1 10
V10

b D V8
c
8 d V13
LP V11

11
V12 3
1

Figure 6a – General view of a Toepler Figure 6c – Example of oil introduction

pump extraction apparatus by bottle
IEC 2462/11

Key
V1 – V11 hand stopcocks
1 mercury reservoir – 2 l V10 – V12 non-return valves
2 gas collection flask – 1 l V13 electromagnetic three-way valve
3 degassing flask – 250 ml or 500 ml VP1 rough vacuum pump
4 gas-collecting burette – 25 ml (0,05 ml divisions) VP2 main vacuum pump
5 introduction of oil sample via syringe LP connection to low pressure air (± 110 kPa)
6 Pirani vacuum gauge SL connection to GC sample loop
7 mercury-levelling vessel CG connection to calibration gas cylinder
8 magnetic stirrer abc electrical contacts
9 septum d mercury level mark on tube
10 oil-sampling bottle A connection to rough vacuum pump and air
11 jet B Connection to main vacuum pump
C Connection to mercury-levelling vessel
D connection to waste oil reservoir and rough
vacuum pump
NOTE Item 6 of Figure 6a should read “capacitance measurement device”.

Figure 6 – Example of a Toepler pump extraction apparatus

 BS EN 60567:2011
– 24 – 60567 © IEC:2011

7.2.3 Extraction procedure

The following is a typical extraction procedure used when a sample is in a syringe. It is

described by reference to the apparatus shown in Figures 6a and 6b. Modifications in the
procedure may be needed for apparatus of other designs.

a) Weigh the syringe (5) containing the oil sample and connect it to the degassing flask (3).
When a bottle is used as a container (Figure 9c), the mass of oil degassed is determined
by weighing the degassing flask before and after introducing the oil.
b) Open valves V1, V2, V4, V6, V7 and V9. Close valves V3, V5 and V8. The valve V13 is a
solenoid-operated three-way valve, which at this stage is not energized and connects the
vacuum pump VP1 to the system.
c) Switch on the vacuum pumps VP1 and VP2 and the magnetic stirrer (8).
d) When the pressure has fallen to 10 Pa, close valves V2, V6 and V7.
e) Open valve V8 and inject a sufficient oil sample through the septum (9) into the degassing
flask (3). This is the start of the degassing part of the Toepler pump cycle.
NOTE 1 A gas bubble in the syringe suggests that the plunger has stuck and indicates the desirability of a
new sample. If this cannot be provided, ensure that the bubble is introduced together with all of the oil or is
re-dissolved in the oil by shaking the syringe.

NOTE 2 The minimum oil volume to be used is the volume necessary to produce enough gas volume for
injection in the gas chromatograph. When this is possible, larger oil volumes may be used to increase the
precision of the analysis. For oil from a factory test, a modification may be needed; see note 3 of step j) below.

f) After the established degassing time (for example, 1 min to 3 min) continue the first
Toepler pump cycle by switching valve V13 so as to admit low-pressure compressed air
above the mercury which rises to the level of contact (a), compressing gas from the
collection flask into the burette. Reversal of valve V13 to connect the vacuum pump to the
mercury reservoir (1) allows the mercury to return (the gas collected in the burette being
trapped by the non-return float valve V10) and further gas to be extracted from the oil. The
contacts allow this cycle to be automated. Inductive level switches may be used instead.
An electric counter is helpful in counting the number of cycles and for stopping the
procedure after the required number of cycles, as established as standard for the
apparatus. Alternatively, the equipment may be run automatically for a standard time (for
example, 10 min for a cycle time of 1 min).
The number of strokes should be such that the vacuum at the end of extraction
approaches the initial value before extraction. The number of strokes necessary depends
on the ratio between the total volume of the equipment and the volume of the pump.
Typically, 4 to 20 strokes have been found suitable to reach 97 % extraction for the more
soluble gases, depending on the equipment used.
g) Switch off the automatic cycling control (if used) and set valve V13 to admit air. Allow
mercury to rise into the burette to above the level of valve (V5). Close valve (V4).
h) Open valve (V6) and adjust the mercury levelling vessel (7) to bring the mercury surfaces
to the same level. Read the total volume of gas collected in the burette. Note the ambient
temperature and pressure.
i) Remove and reweigh the oil syringe to obtain the mass of oil that has been degassed.
Determine the density of the oil at ambient temperature.
j) Close valve (V1), open valve (V2) to admit the extracted gas into the sample loop. Again
adjust the mercury levelling vessel to bring both the mercury surfaces to the new level and
close valve.
NOTE 3 Another arrangement frequently used is to fit a septum on the top of the burette in place of valve
(V2) and to transfer an aliquot of gas to the chromatograph by means of a precision gas-tight syringe. In such
a case, it is good practice to fit a new septum each time the equipment is used.

NOTE 4 If an inadequate quantity of gas has resulted from degassing the first oil sample, the degassing flask
may be disconnected and emptied, and the method repeated with a new oil sample. The first quantity of
extracted gas is retained in the burette by keeping valve (V4) closed until the remainder of the system is re-
evacuated (step d) above).
BS EN 60567:2011
60567 © IEC:2011 – 25 –

Alternatively, where concentrations of gas are expected to be low, a larger degassing

flask, up to 2 l, may be fitted, with sample volumes up to 500 ml. Introduce the oil sample
slowly to facilitate gas extraction.
k) Calculate the total gas content extracted C T of the oil sample in µl/l at 20 °C and
101,3 kPa from the expression:

C T = (P 101,3 ) × (293 273 + t ) × (Vd m ) × 10 6

where
P is the ambient air pressure, in kPa;
t is the ambient air temperature, in °C;
V is the total volume of gas extracted, at ambient temperature and pressure, in ml;
d is the density of oil corrected to 20 °C, in g/ml;
m is the mass of oil degassed, in g.
l) Carry out the analysis as in Clause 8.
NOTE 5 Because the gas is not totally extracted from the oil, a rinse step may be required after a high
concentration has been run (for example, after analysis of oil sample from tap changer). The extractor can be
rinsed with oil containing non-detectable quantities of gases, except for those present in the air.

7.3 Vacuum extraction by partial degassing method

7.3.1 General remark

In this method, gas extraction is accomplished by only one exposure to vacuum (between
3 min for mineral oils and 10 min for the more viscous silicone oils). Extraction efficiency
depends on component gas solubility. Correction of this incomplete gas extraction can be
obtained by calculation from the Ostwald solubility coefficients of the gases in transformer oil,
either mineral or non-mineral (see Annex A)

7.3.2 Partial degassing apparatus

Equipment such as that shown in Figures 6a and 6b is equally suitable for this method with
the following changes:

a) The automatic control arrangements used in the Toepler pump mode (valves V10 and
electric contacts a, b and c) are not required. A simple hand pump (blow-ball) can be fitted
in place of the low-pressure compressed air supply.
b) The total expansion volume (degassing flask (3) plus collection flask (2) and connecting
tubing, less the oil volume) should be at least 20 times the oil volume. In the apparatus
shown in Figure 6b, a collection flask of 500 ml and a degassing flask of 150 ml are
suitable for an oil volume of 25 ml to 30 ml.
c) The mercury reservoir volume should not greatly exceed that of the collection flask; in the
apparatus shown in Figure 6b, a reservoir volume of approximately 600 ml to 700 ml is
recommended. The reservoir should be filled with mercury to leave an air space of not
more than 100 ml to 150 ml.
d) A mark should be made on the dip tube in the mercury reservoir, (mark d in Figures 6a
and 6b) so that when the equipment is used for partial degassing the mercury can be
brought to this mark and the expansion volume thus accurately defined.
e) The apparatus shall be leak-free and capable of evacuation to 0,1 Pa. The burette,
typically 3,5 ml, shall be calibrated in 0,01 ml divisions, and the connecting tubing and
vacuum gauge as in points d) and f) of 7.2.2.
f) Alternatively to the syringe, the needle and the septum, a flexible PTFE tubing connected
to the valve can be used to introduce oil samples.
 BS EN 60567:2011
– 26 – 60567 © IEC:2011

7.3.3 Extraction procedure

a) Weigh the syringe (5) containing the oil sample and connect it to the degassing flask (3).
b) Proceed as in steps b) to e) of 7.2.3, evacuating down to 0,1 Pa.
c) Allow degassing to continue for 5 min to 10 min, depending on the oil viscosity, with the
stirrer operating vigorously. Then close valve (V9).
d) Proceed as in steps g) and h) of 7.2.3.
e) Calculate the total gas volume extracted by dividing the volume of gas collected in the
burette by the volumetric collection ratio V c / V t , where
– V c (collection volume) is the volume of the burette and collection flask (2), from mark
“d” to valves V9, V6, V5 and V2;
– V t (total expansion volume) is V c plus the volume of the degassing flask (3) and
connecting tubing to V9, V8 and V7, less the volume of oil.
f) Remove and reweigh the syringe to obtain the mass of oil that has been degassed.
Determine the density of the oil at ambient temperature.
g) Correct the calculated total volume of gas extracted to 20 °C and 101,3 kPa as in step k)
of 7.2.3.
h) Inject an aliquot of the gas extracted into the chromatograph as in step j) of 7.2.3.
i) Carry out the analysis as in Clause 8.
j) Calculate the actual concentration of each gas component originally present in the oil
sample, by dividing its chromatographically measured concentration by its extraction
efficiency E i (see Annex A).
NOTE Because the gas is not totally extracted from the oil, a rinse step may be required after a high
concentration has been run (for example, after analysis of oil sample from tap changer). The extractor can be
rinsed with oil containing non-detectable quantities of gases, except for those present in the air.

7.4 Stripping extraction method

7.4.1 General

The extraction of dissolved gases is carried out by the carrier gas itself bubbling through a
small volume of the oil. Typically an oil volume between 0,25 ml and 5 ml is used.

The time required to extract larger volumes would give unacceptable gas chromatograms
except when used with cold traps or for hydrogen analysis only.

7.4.2 Stripping apparatus

Various designs of strippers are used. Figure 7 shows borosilicate glass strippers. Oil is
injected into the stripper from a syringe via a rubber septum. This septum can be used several
times (3 to 10 depending on the size of the needles) before leakage occurs.

A design of a stripper made of stainless steel is shown in Figure 8. A needle with a cock and
interchangeable syringe connection is permanently fixed into the base of the stripper and a
syringe containing oil is attached to the fixed needle. The oil is injected by the movement of a
pneumatic actuator on the syringe plunger.

The volume of oil injected shall be measured with an accuracy better than 1,0 %. Injection
from a precision syringe has been found to achieve this requirement but difference of syringe
mass before and after injection is to be preferred if better accuracy is required.
BS EN 60567:2011
60567 © IEC:2011 – 27 –

13

22 mm
3
135 mm

28 mm
13

Figure 7b – Example 1 of stripper

for general analysis

13

45 mm
75 mm

Figure 7c – Example 2 of stripper

for general analysis

Figure 7a – Stripper for hydrogen analysis

IEC 2463/11

Key
1 glass indentations 3 oil injection septum
2 capillary tube 13 connection to six port gas-sampling
valve (see Figure 12a)

Figure 7 – Types of glass strippers

 BS EN 60567:2011
– 28 – 60567 © IEC:2011

13

14
6

5 8
780 mm

2 10
300 mm

3
4 9
11

12

7
480 mm

IEC 2464/11

Key
1 stainless steel tube (OD 6 mm – ID 4 mm) 8 end of oil injection needle
2 heating blocks 9 air cylinder
3 temperature sensor 10 oil injection
4 5 ml syringe 11 three-way valve
5 aluminium bracket 12 stopcock
6 stainless steel capillary tubing inlet and outlet 13 connection to six port gas-sampling valve
(OD 1,6 mm) (see Figure 12a)
7 waste oil 14 biconical union
Figure 8 – Stainless steel stripper
BS EN 60567:2011
60567 © IEC:2011 – 29 –

7.4.3 Outline of procedure

a) As shown in Figure 9a connect the stripper in place of the sample loop of the gas
chromatograph gas-sampling valve preferably using compression fittings. Vacuum rubber
tubing may alternatively be used for the connections then verify that there is no leakage
due to overpressure of the carrier gas; if such is the case, reduce the overpressure.
b) Maintain the stripper at a controlled temperature between 20 °C and 80 °C. Indeed,
elevated temperatures reduce oil viscosity and facilitate gas stripping.
c) Allow the carrier gas to flow through the stripper.
d) Before injection of the oil, check that the operating conditions of the equipment are
satisfactory and particularly that the baseline on the recorder is stable.
e) Inject the oil to be analysed into the stripper. The volume of oil to be injected will depend
upon the type of stripper used and the expected gas content. During this operation, the
carrier gas flow through the stripper shall be maintained.
f) After the analysis has been completed, some stripper designs permit a back flush of the
injected oil to waste without disconnecting the stripper. If the stripper is to be
disconnected for cleaning, the gas outlet tube should be disconnected first to avoid the
possibility of the oil sample entering the gas-sampling valve. Carry out the analysis as in
Clause 8.

1 1
A
B
5 5
B A
A B
4 C
2
2 3 3
2

Position A: analysis Position A1: trapping of gases

1 1
A
B

5 5
B A A B
4
C
2 2
3 2 3

Position B: purge (emptying of stripper) Position B1: injection + purge (emptying of stripper)

Figure 9a – Usual arrangement for degassing Figure 9b – Arrangement with cold trap added for use
up to about 2,5 ml of oil with larger quantities of oil

IEC 2465/11

Key
A inlet carrier gas 1 stripper
B outlet carrier gas (to chromatograph) 2 six port gas-sampling valve
C carrier gas for extraction 3 mercury valve
4 cold trap
5 waste vessel

Figure 9 – Schematic arrangement for connecting an oil stripper

to a gas chromatograph
 BS EN 60567:2011
– 30 – 60567 © IEC:2011

7.5 Headspace method

7.5.1 Principle of the method

In this method a volume of oil V L is introduced in a glass vial in contact with a gas phase
(“headspace”) of volume V G . A portion of the gases dissolved in the oil (H 2 , O 2 , N 2 , CH 4 ,
C 2 H 2 , C 2 H 4 , C 2 H 6 , CO and CO 2 ) transfers to the headspace, under equilibrium conditions of
temperature, pressure and agitation. The headspace is transferred to an injection loop or
directly in the column of the gas chromatograph depending on the apparatus used. Calibration
curves are used to establish the concentration of each gas in the headspace. The
concentrations of the gases in oil are then calculated by using Henry’s law and experimentally
determining the partition coefficients of the oil or by direct calibration with gas-in-oil
standards. A schematic representation of this method is shown in Figure 10.

Warning: This method will provide reproducible results only if all the operation and calibration
parameters are precisely controlled, otherwise significant errors may occur. The following
parameters are of particular importance: total volume of vials, volume of oil, tightness of
septa, temperature, dilution with argon and actual pressure in the vials after each step of the
procedure. The same exact parameters should always be used for field samples, gas
standards and oil standards.

6
5
8
7 7

1
IEC 2466/11

Key
1 vial 5 carrier gas
2 septum 6 pressurization gauge
3 oil sample 7 headspace sampler needles
4 gas phase 8 to GC injection loop and detectors

Figure 10 – Schematic representation of headspace sampler

7.5.2 Symbols and abbreviations

V total volume of the vial;
VG volume of the gas phase in the vial;
VL volume of the oil phase in the vial;
CG concentration of gas (i) in the gas phase of vial, obtained by GC (gas
chromatography);
CL0* concentration of gas (i) in the oil sample, obtained directly from C G using calibration
curves with gas-in-oil standards;
P, t atmospheric pressure and temperature when the oil sample was analysed (P in kPa; t
in °C);
BS EN 60567:2011
60567 © IEC:2011 – 31 –

Ps, ts atmospheric pressure and temperature when the gas-in-oil standard, or the gas
standard, was analysed (P s in kPa; t s in °C);
K partition coefficient of gas (i), for the calculation of CL0 using gas standards;
CL0 concentration of gas (i) in the oil sample.

7.5.3 Headspace extraction apparatus

7.5.3.1 General remark

An example of a suitable design includes the following components.

7.5.3.2 Headspace sampler

This sampler is equipped with a transfer line connected directly or through a T union to the
first column of the gas chromatograph. Samplers equipped with syringe injection have not
been evaluated.

NOTE The size of injection loops should be adapted to the type of columns in order to avoid broadening of peaks.
If injection loops larger than 1 ml are used, it should be verified that the overpressure is high enough to adequately
flush the sample loop and fill it to atmospheric pressure prior to the injection step (this will depend on the volume
of the circuit between the vial and the vent in some systems).

A second injection loop may be necessary for injecting gas mixtures directly into the
chromatograph, to check the response of the GC detectors daily with calibrated gas, and to
perform Buchholz analysis. These operations are also possible using the headspace sampler,
after transferring the calibrated gas mixture or the Buchholz gas sample into pre-purged vials.

7.5.3.3 Headspace glass vials

7.5.3.3.1 General

Use headspace vials suitable for use with the equipment. The actual volume of commercial
vials may differ from the nominal value.

NOTE 20 ml vials have shown good performance. Their actual volume is closer to 22,3 ml.

The total volume of the vial V has a great influence on the value of the V G /V L ratio, and on the
final results. Since significant variations of volume can occur between different batches of
vials and between different vials of the same batch, the average value for each batch of vials
purchased by the laboratory should be determined when they have different batch numbers.
This can be done by measurement of the mass of pure water that can be contained in a vial
according to the procedure described below in 7.5.3.3.2.

Condition 10 to 20 vials from the same batch and 100 ml of distilled water for 1 h at room
temperature and note the temperature.

7.5.3.3.2 Headspace glass vials calibration procedure

Determine the weight of the empty vials to the nearest 0,01 g. Fill the vials completely with
distilled water as shown in Figure 11 and reweigh to the nearest 0,01 g. Calculate the volume
of each vial by using the following equation:

V = (W − W0 ) D

where
V is the total volume of the vial, in ml;
Wo is the weight of the empty vial, in g;
W is the weight of the vial filled with water, in g;
 BS EN 60567:2011
– 32 – 60567 © IEC:2011

D is the density of water at measurement temperature, in g/ml.

Calculate the mean volume and the relative standard deviation, s % for the vials tested. If the
value of s % is higher than 1 %, the controlled batch of vials is rejected and a new batch of
vials shall be tested .

IEC 2467/11

Figure 11 – Vial filled with water

7.5.3.4 Septa

The brands of septa used should not introduce contamination of the vials during analysis and
should not leak after having been punctured by needles, especially by the large diameter
needles in 7.5.4.1.2.

The suitability of septa is checked by analysis on blank vials containing argon only at
atmospheric pressure, having been punctured the same number of times as the vials
containing the oil samples or gas standards and left 24 h at room temperature. Very low
quantities of oxygen and nitrogen should be found (not more than 150 µl/l O 2 and 350 µl/l N 2 ).

Another means of checking septa is by immersing the closed vial with its pierced septum in a
water bath heated at 90 °C and check for bubbles This test is useful also for checking the
crimping method.

Porosity of septa can also be tested by filling a number of crimped vials (at least 10) with a
gas mixture containing approximately 100 µl/l hydrogen using one of the methods within
7.5.4.1. Using the method in 7.5.5.3, analyse duplicate vials for hydrogen content at intervals
over a period of about 1 week, the first analyses being made as soon as possible after filling
the vials. Normal calibration procedures should be carried out. The septum and seal are
acceptable if the rate of decrease in hydrogen concentration is less than 2,5 % per day.

NOTE 1 Only PTFE-lined septa should be used, preferably of the chlorobutyl rubber, high-temperature type
(PTFE = polytetrafluoroethylene = Teflon ®). Silicone rubber septa have been found to leak and should be avoided.
BS EN 60567:2011
60567 © IEC:2011 – 33 –

In any case, new types of septa should be checked before use. The quality of the crimping equipment (crimping
head and perforated aluminium caps) and the skill of the operator have been reported as critical.

NOTE 2 When the reliability of septa cannot be assessed with certainty, it is recommended that subprocedure
7.5.4.1.1 (preparation of vials in an inert box) be used.

7.5.3.5 Oil syringes

Appropriate oil volumes, measured as precisely as possible, are introduced in the vials, so
that the V G /V L ratio is the same for all field samples and gas-in-oil standards analysed.
Volumes of 10 ml to 15 ml have been found suitable, but lower or larger oil volumes may be
used, depending on the gas content of the oil sample. Glass syringes of 20 ml, 30 ml or 50 ml
can be used. New batches of syringes should be calibrated with the following procedure.

Fill a syringe with 20 ml of oil of known density. Weigh the filled syringe to the nearest 0,01 g.
Draw 15 ml of oil from the syringe then reweigh the syringe. Subtract the two weights to
obtain the weight of oil drawn. Calculate the volume of oil by dividing the weight of oil by the
density of the oil. Perform this test on 20 syringes of each new batch. Calculate the standard
deviation(s) and s % for the 20 syringes. If s % is higher than 1,3 %, the controlled batch of
syringes is rejected and a new batch of syringes shall be tested.

Glass syringes are not intended for precise volumetric work. The index mark on the piston is
about 0,5 ml in width, allowing considerable variations with operators. Therefore, the exact
amount of oil introduced in a vial should be measured by weighing the vial or the syringe
before and after introduction of the oil (see 7.5.4.1).

Two different types of needles are needed (A and B). For type A, 0,84 mm ID (gauge 18) (for
the transfer of oil) and for type B, 0,25 mm ID (gauge 26) (for the transfer of gases and
pressure equilibration) have been found suitable. Needle size should be adapted to the type
of septa to ensure that they will not induce leaks (see 7.5.3.4).

For the procedure of 7.5.4.1.2, a maximum size of 0,84 mm ID and 1,27 mm OD (gauge 18) is
recommended to avoid leaks through the septa.

For the procedure of 7.5.4.1.1, larger size needles may be used as they will not be used to
pierce septa, and a larger size needle will facilitate oil introduction.

7.5.3.6 Inert boxes

7.5.3.6.1 General

An inert box (either a glove box, a glove bag or a “revolving table”) is required for the
procedure of 7.5.4.1.1.

7.5.3.6.2 Glove box

The glove box and its lock chamber should be purged with at least 5 times its volume of argon
(typically, at 400 ml/min). Alternatively, a plastic glove bag, filled with all the necessary
equipment (syringes, vials, etc), then purged with argon, may be used.

7.5.3.6.3 Revolving table

The “revolving table” is described in Figure 12: a carousel carrying 20 empty vials is placed in
a circular housing, hermetically covered by a transparent removable lid. The carrousel can be
rotated from outside with a knob.

A septum is attached to one side of the lid, and a vial crimper on the other side, both facing
the mouth of the vials.

The revolving table is continuously flushed with inert gas (the same used as carrier gas) at a
known and constant flow rate and pressure, to ensure constant operation conditions.
 BS EN 60567:2011
– 34 – 60567 © IEC:2011

2
9
4

10
1
IEC 2468/11

Key
1 housing 6 lid septum
2 lid 7 oil syringe
3 rotating carousel 8 vial septum and cap
4 argon purge 9 vial crimper
5 vial 10 vial lifter
Figure 12 – Revolving table

7.5.3.7 Headspace operational conditions

See Table 2. The same conditions can be used for mineral and non-mineral oils.
BS EN 60567:2011
60567 © IEC:2011 – 35 –

Table 2 – Examples of headspace operating conditions

Carrier gas Argon

Temperatures, in °C Vial 70
Transfer line 70-150
Injector 150
Pressure, in kPa Overpressure in vial 35-40
Volume, in ml Sampling loop 0,25-1
Times, in minutes Equilibration 10-180
Pressurization 0,05-0,25
Pressure equilibrium 0,05-0,25
Expansion in sample loop 0,20-0,25
Injection 0,20-1,00
Mixing power High
NOTE 1 Ultrasonic agitation should not be used to speed up
equilibrium times as it may produce hydrogen.
NOTE 2 ”High” (or “maximum”) mixing power refers to the position on
the headspace equipment (about 100 shaking movements per minute).
NOTE 3 The pressurization time to be used is the shortest one to get
equilibrium.

Monitoring/recording of measurable parameters (argon overpressure, temperature, etc.) within

a precision of ± 0,5 % is advisable to verify if they have not changed accidentally during an
extended run.

This can be done by recording or printing the electronic reading of pressure available within
the headspace equipment during the analysis. This may need important modifications for
some headspace samplers that have only mechanical reading of the pressure.

Atmospheric pressure and ambient temperature shall be recorded when filling the vials, within
a precision of ± 0,5 %, to be able to calculate actual quantities of gases introduced at the
various steps of the procedure, and/or to convert to the conditions of this standard.

7.5.3.8 Gases

Argon used shall be chromatography graded (typically, > 99,999 % pure).

Standard gas mixtures supplied with a calibration certificate of ± 1 %, if available, or at worst

± 2 %, are used to establish a calibration curve for each dissolved gas. The concentrations of
the mixtures should be chosen in order to fully cover the expected concentration range of field
samples, which depends on the type of equipment to be monitored.

Different levels of concentrations in the calibration curve may be obtained by injecting

different volumes of the same standard mixture or by using different standard mixtures in a
suitable concentration range.

7.5.4 Headspace extraction procedure

7.5.4.1 Preparation of vials

Two alternate methods are possible, using either an inert box or needles.
 BS EN 60567:2011
– 36 – 60567 © IEC:2011

7.5.4.1.1 Preparation of vials in an inert box

This method has the advantage that septa are never punctured before being placed in the
headspace carrousel. The risk of septa leak (with its dramatic effect on analysis results) is
therefore much reduced.

7.5.4.1.1.1 Pre-purging of vials

Pre-purging can be carried out

a) in the glove box: for practical reasons, series of 10 samples are prepared. Label and
weigh 10 vials with their corresponding perforated aluminium caps and septa (uncrimped)
to the nearest 0,01 g. Place the 10 weighed vials, 10 glass syringes of 20 ml, and 10 oil
samples in their glass syringes or glass ampoules in the lock chamber of the glove box.
Purge the lock chamber with argon. Transfer the content of the lock chamber into the
glove box filled with argon.
b) in the revolving table: up to 20 empty vials weighted as above and their corresponding
caps and septa (of known average weight) are placed in the closed housing. Purge with
argon for 10 min to 15 min.

7.5.4.1.1.2 Preparation of vials with oil samples

Vials with oil samples can be prepared as follows:

a) in the glove box: with a 3-way valve transfer about 5 ml of the first oil sample into a glass
syringe and rinse the entire body of the syringe with the oil. Release the 5 ml oil to waste
and fill the glass syringe with 20 ml of oil. Disconnect the oil syringe or glass ampoule and
fix a needle to the glass syringe.
Release about 5 ml of oil into the waste vessel, then fill an empty vial with the remaining
15 ml of oil with the tip of the needle to the bottom of the vial. Adjust the volumes if a
lower final oil volume (between 10 ml and 15 ml) has been chosen.
Close the vial with its septum and crimping cap and crimp with the help of the crimping
bead, making sure that the lined side is turned towards the inside of the vial.
NOTE 1 Closing the vial should be done within 45 s after the vial has been filled with oil; otherwise, the
sample should be discarded and a new one prepared.

Repeat the same procedure for the other nine samples.

b) in the revolving table: connect a needle to the syringe containing the oil sample. Release
about 5 ml of the oil sample into the waste vessel, to condition the needle and remove
traces of air bubbles. Introduce an aliquot (10 ml to 15 ml) of the oil sample in a vial
through the septum of the lid. Rotate the carousel and move the caps on the top of the
vials. Rotate the carousel again and crimp the vial using the crimper and vial lifter. Repeat
the same procedure for the 20 vials, then stop the flushing, open the lid and remove the
vials from the carousel.
c) Take the crimped vials out of the glove box or revolving table and weigh them to the
nearest 0,01 g. Calculate the mass of oil by subtracting the weight of the empty vials from
the weight of the filled vials and calculate their volumes by dividing the mass by the
density of the oil.
NOTE 2 The actual density of oil (measured according to ISO 3675 or other standardized method) should be
used for the calibration procedure with gas-in-oil standards. For sample analysis, an average density of the oil
type (for example, one for paraffinic oils and one for naphthenic oils) should be used.

Measure the pressure and the ambient temperature in the glove box or revolving table
precisely. Place the oil-filled vials in the headspace carousel for analysis.

The same procedures apply to gas-in-oil standards.

BS EN 60567:2011
60567 © IEC:2011 – 37 –

7.5.4.1.1.3 Preparation of vials with gas standards

This is effected outside the glove box or revolving table. Place a piece of paraffin film
(Parafilm ®) 1 on the mouth of a vial. Insert two needles through the film. Purge with
calibrating gas mixture so that the purging volume of the vial is at least 5 times the volume of
the vial (typically, 1 min at 100 ml/min). Remove the needle and close the vial with a septum
and crimp cap, without removing the film.

7.5.4.1.2 Preparation of vials with needles

Crimp a series of vials using perforated aluminium caps fitted with a PTFE-lined septum.
Ensure that the lined side is turned towards the inside of the vial and that the latter is properly
sealed by trying to turn the cap. If the cap is not tightly fixed, repeat the process.

7.5.4.1.2.1 Pre-purging of vials

Insert two needles A (7.5.3.5) through the vial septum, one to be used as inlet gas and the
other as outlet gas, on the sides of the septum, not in its centre. Purge each vial with argon at
least 5 times the vial volume (for example, at a rate of 1 l/min for 0,1 min at 120 kPa or
120 ml/min for 1 min).

First remove the outlet needle and then the inlet needle, to build up some argon overpressure
in the vial. Removal of the outlet and inlet needle should be done with a minimum of delay in
order to avoid excessive overpressure if high flushing rates are used.

The efficiency of this preparation technique can be checked by analysis of one of these vials
containing only argon. This has also been used to test the quality of septa (see 7.5.3.4). Very
low quantities of oxygen and nitrogen should be found (see NOTE 2 of 7.5.3.4).

7.5.4.1.2.2 Preparation of vials with gas standards

Insert two needles A (7.5.3.5) through the vial septum, one to be used as inlet gas and the
other as outlet gas. Purge one vial with each calibration gas mixture at the same rate used in
7.5.4.1.2.1.

First remove the outlet needle (overpressure will take place in the vial). Remove the inlet
needle. Using a 10 ml syringe with a type B needle remove the overpressure in the vial by
inserting the needle of the syringe through the septum. After equilibrium, the atmospheric
pressure will be obtained. If not, the dilution factor, and the results, will be affected when
argon overpressure is applied at the next stage.

Measure ambient temperature and atmospheric pressure precisely in order to determine the
exact quantities of gases present in the vial, and/or to convert to normal conditions (20 °C;
101,3 kPa).

7.5.4.1.2.3 Preparation of vials with oil samples

Weigh a pre-purged crimped vial. Attach a type A needle to the syringe stopcock. Insert the
needle through the septum and insert simultaneously a second type B needle to release the
argon overpressure.

Fill up the vial with the chosen amount of oil. Remove the two needles together, to make sure
that the pressure in the vial at this stage is atmospheric pressure.

___________
1 Parafilm ® is the trade name of products supplied by Pechiney Plastic Packaging Company. This information is
given for the convenience of users of this standard and does not constitute an endorsement by the IEC of the
products named. Equivalent products may be used if they can be shown to lead to the same results.
 BS EN 60567:2011
– 38 – 60567 © IEC:2011

Weigh the oil-filled vial and subtract the weigh of the empty vial to get the mass of oil in the
vial. Divide by the density of the oil to get the exact volume of oil in the vial.

The same procedure applies for vials of gas-in-oil standards.

7.5.4.2 Headspace analyses

Place the vials inside the headspace sampler and begin the analysis using operational
conditions such as those given in Table 2 as examples. As shown in Table 2, a large range of
temperatures is possible for the transfer line and the injection valve, as well as for the
equilibration times needed, depending on the exact type of equipment used.

NOTE Pressure in the vials at this stage should always be below the injection pressure (1,4 bar). Pressure in the
glove box may exceed this, in which case it should be measured (in the glove box, or in the vial, with the gauge on
the headspace equipment) and reduced if necessary. Ideally, it should be close to atmospheric pressure and
should be known with precision in order to make corrections and calculations indicated in 7.5.5.2 and 7.5.5.3.

Record the actual atmospheric pressure throughout the run, since it may vary by several per
cent over an extended run, especially if unattended, and it may be necessary to make
corrections to total pressure in the vial.

7.5.4.3 Procedure for analysis at low concentration levels

The procedures described in 7.5.4.1 and 7.5.4.2 provide the detection limits specified in
Table 5 for service tests. More sensitive procedures (and special attention to avoid
contamination) are required to obtain the detection limits specified for acceptance tests,
where extracted gases in the headspace of the vials are in the nl/l range.

Toepler and partial degassing, where extracted gases are in the µl/l range at these levels, are
more recommended for acceptance tests. However, if headspace is to be used for low
concentration levels and acceptance tests, the more sensitive equipment and procedures
described below are required:

– capillary GC columns such as the PLOT columns described in 8.3.2;

– reduced dead volumes between the vial and the GC detectors;
– calibration with different calibration curves;
– manual (rather than electronic) integration of the baseline of GC peaks. This will lower the
detection limits to typically 0,2 µl/l for hydrocarbons;
– for the still lower detection limits of acceptance tests, a larger injection loop of 1,5 ml,
followed by a split of the gas sample between the vial and the GC columns (typically, of
1/50 to 1/100). This will result in much sharper GC peaks (particularly for hydrogen);
NOTE The equipment may be instructed to automatically choose the splitter option (for example, 1/100 for
acceptance tests and 1/10 for service tests).

– alternatively, a syringe may be used to manually transfer a gas sample from the vial to the
injection port of the GC. This will eliminate the gas dilution resulting from Argon
pressurization of the vial.

7.5.4.4 Procedure for analysis at high concentration levels

It has been observed that when hydrogen concentration levels are too high, the measured
values are considerably below actual values. In such cases, a smaller volume of the oil
sample should be used to obtain accurate results.

It has been found that when the hydrogen content is typically above 6 000 µl/l, a second
sample with 7 ml of the oil sample in the vial and a third measurement with 3 ml in the vial
should be performed. Valid results are obtained when identical values with two different
dilution factors are measured.
BS EN 60567:2011
60567 © IEC:2011 – 39 –

When using procedure 7.5.5.2 (calibration with gas-in-oil standards), introduce the reduced
volume of oil sample (7 ml or 3 ml) in a syringe, complete to 15 ml with degassed oil, then
transfer into a vial and proceed as with regular oil samples. Multiply the measured values of
gas in oil by the proper oil dilution factor (15/7 or 15/3).

When using procedure 7.5.5.3 (calibration with gas standards), introduce the reduced volume
of oil in a vial and proceed as with regular oil samples. Calculate gas concentrations in the oil
sample using the equation indicated in 7.5.5.3 and the proper values of V G and V L .

NOTE This non-linearity has been observed mainly with hydrogen dissolved in oil, but samples with high
concentrations of the other dissolved gases should also be measured following a similar procedure.

7.5.5 Calibration of the headspace extractor

7.5.5.1 General remark

Two different calibration methods are available.

7.5.5.2 Calibration with gas-in-oil standards

This is the preferred method of calibration recommended by CIGRE TF D1.01.15.

The advantage of this method is that partition coefficients need not be determined. Neither is
it affected by the linearity problems evidenced by the scatter of results observed during
CIGRE inter-laboratory tests using partition coefficients.

Three gas-in-oil standards at different concentrations, prepared according to the methods

described in 6.2 or 6.3, are run at least once a month or each time an operational parameter
has changed (argon overpressure, new batches of vials or syringes) or if calibration of GC
detectors with gas standards indicate a change in the response of detectors.

Direct calibration curves are drawn, relating peak height or peak area to the concentration of
gases in the gas-in-oil standard.

When an unknown oil sample is run under exactly the same operational conditions, its
dissolved gas concentrations CL0* can be obtained by using the above calibration curves. A
small correction for the differences of atmospheric pressure and temperature when the gas-in-
oil standard and unknown oil samples were analysed should be made:

CL0 = CL0 * × (P Ps ) × [(273 + ts ) (273 + t )]

(see 7.5.2 for abbreviations).

7.5.5.3 Calibration with gas standards

The advantage of this method is that there is no requirement to prepare gas-in-oil standards
for direct calibration of the headspace extractor.

Partition coefficients need to be determined accurately, however, under exactly the same
operational conditions as the oil samples (see 7.5.5.4).

A vial containing the gas standard, prepared according to 7.5.4.1.2.2, is placed in the
headspace sampler and analysed through the headspace injection loop.

Calibration curves relating peak height or peak area to the concentration of the gases in the
gas standard are drawn. When an oil sample is run under exactly the same operational
 BS EN 60567:2011
– 40 – 60567 © IEC:2011

conditions, the concentration of the gases in the gas phase C G can be obtained by using this
calibration curve.

The concentrations in the oil sample are then determined using the following equation, based
on Henry's law, which requires that the partition coefficients K and the actual vial volume ratio
(V G /V L ) for each oil sample be precisely determined.

CL0 = C G × (K + VG VL )

NOTE 1 V L and V G are calculated according to 7.5.3.3.2 and 7.5.3.5.

A correction for atmospheric pressure and temperature should be made using Equation (1)
(see 7.5.5.2), replacing “gas-in-oil standard” by “gas standard”. Generally, gas standards are
prepared together with oil samples and so the temperature and pressure inside the vials
before headspace extraction should be the same. Concerning the atmospheric pressure, it
can vary during the time needed for analysing several samples; as a consequence, in some
systems equipped with sample loops in equilibrium with atmospheric pressure, the amount of
gas (number of moles) going to the detector through the sample loop can change. Because of
this, the correction for atmospheric pressure should be made.

NOTE 2 Although it is not needed for calibration, it is recommended when using this procedure that the overall
performance of the extractor be verified regularly by running gas-in-oil standards.

7.5.5.4 Determination of partition coefficients

The recommended method of determination of partition (or Ostwald or solubility) coefficients

is the CIGRE TF D1.01.15 method consisting of bubbling pure gases in the oil according to
ASTM Method D2780, or bubbling a standard mixture of gases in the oil.

It has been shown by CIGRE that partition coefficients measured by different laboratories
using the headspace method and gas-in-oil standards, and/or the so-called slope/intercept
method are not reliable and reproducible.

Examples of partition coefficients measured experimentally at 70 °C are given in Table 3.

Table 3 – Headspace partition coefficients at 70 °C in mineral insulating oil

Mineral oil
Density 0,864
H2 0,074
O2 0,17
N2 0,11
CH 4 0,44
CO 0,12
CO 2 1,02
C2H2 0,93
C2H4 1,47
C2H6 2,09
C3H6 5,04
C3H8 5,37
C4H6 10,10
BS EN 60567:2011
60567 © IEC:2011 – 41 –

8 Gas analysis by gas-solid chromatography

8.1 General remarks

Gas samples, whether obtained from gas-collecting relays or removed from an oil sample, are
analysed by gas chromatography. The gases to be determined are as follows:

– Hydrogen H2
– Oxygen O2
– Nitrogen N2
– Methane CH 4
– Ethane C2H 6
– Ethylene C2H 4
– Acetylene C2H 2
– Carbon monoxide CO
– Carbon dioxide CO 2

For the purpose of this guide, C 3 hydrocarbons are not required, but they may on occasion
give useful information.

A number of methods may be used for the analyses; the two methods detailed in Table 4 are
given as examples that have been found suitable for all extraction techniques.

The following assumes a measure of competence in the techniques of gas chromatography

and omits, for brevity, many details that may be found in practical manuals on these
techniques.

Table 4 – Examples of gas chromatographic operating conditions

Example 1 Example 2
Type of columns Packed PLOT
Column 1 Porapak N ® 2 or Haysep N Carboxen 1 006 ® 4 or
® 3,
Carboplot P7 ® 5,
L=3;D=3
L = 30 ; D = 0,5
Column 2 Molecular sieve 5A or 13x Molecular sieve 5A (50 µm)
L = 0,5 ; D = 3 L = 30 ; D = 0,5
Temperature (°C) of:
Column bypass valve 120 90

___________
2 Porapak ® is the trade name of products supplied by Water Associates. (Porapaks ® are porous polymer beads
modified to give different retention characteristics. Eight types are available; in order of increasing polarity
these are Porapak ® P, PS, Q, QS, R, S, N, and T). Haysep ® products are polymers of a similar type. This
information is given for the convenience of users of this standard and does not constitute an endorsement by
the IEC of the products named. Equivalent products may be used if they can be shown to lead to the same
results.
3 Haysep N ® is the trade name of products supplied by VICI Valco Instruments. This information is given for the
convenience of users of this standard and does not constitute an endorsement by the IEC of the products
named. Equivalent products may be used if they can be shown to lead to the same results.
4 Carboxen ® is the trade name of products supplied by Sigma-Aldrich. This information is given for the
convenience of users of this standard and does not constitute an endorsement by the IEC of the products
named. Equivalent products may be used if they can be shown to lead to the same results.
5 Carboplot ® is the trade name of products supplied by Agilent Technologies. This information is given for the
convenience of users of this standard and does not constitute an endorsement by the IEC of the products
named. Equivalent products may be used if they can be shown to lead to the same results.
 BS EN 60567:2011
– 42 – 60567 © IEC:2011

Example 1 Example 2
Type of columns Packed PLOT
FID 250 250
HID 250 250
TCD 200 200
Methanator 400 350
Oven 35-180 40-100
Gases separated
On column 1 CO 2 (TCD) C 2 H 4 , C 2 H 2 , C 2 H 6 , CO 2 * (FID)
CO 2 *, C n H n , (FID)
On column 2 H 2 , O 2 , N 2 , CO (TCD) H 2 , O 2 , N 2 , CO (TCD)
CO * (FID) CH 4 , CO * (FID)
Argon carrier gas 25 ml/min 6 ml/min
NOTE L = length (in meters), D = diameter (in mm). * CO and CO 2 converted into CH4 by
methanator.

8.2 Outline of suitable methods using Table 4

In example 1 of Table 4, two separate runs are made, one with a Porapak ® column and the
other with a molecular sieve column. A single detector having adequate sensitivity for all the
gases to be detected is not available; thus, the gases eluted from the column in use are
passed over both a thermal conductivity detector which detects atmospheric gases, CO, CO 2
and H 2 and a flame ionization detector which detects hydrocarbons.

To determine CO and CO 2 with improved sensitivity, a methanator may be fitted at the inlet of
the flame ionization detector to convert CO and CO 2 to methane, which is then detected by
the flame ionization detector.

In example 2 of Table 4, more sensitive PLOT (porous large open tubular) columns are used,
particularly in the case of headspace extraction.

When using a stripping extraction method, it may not be possible to achieve the sensitivity
and precision for hydrocarbons required for factory tests using less than 5 ml of oil. Larger
volumes of oil (10 ml) require longer stripping times to extract the dissolved gases, which
would give unacceptable gas chromatograms unless the extracted gases were to be
concentrated by cold trapping.

The method below is written for an apparatus in which the outputs from the detectors are
switched electrically so that they may be dealt with by a single channel integrator or single
channel chart recorder. Use of a dual channel integrator or recorder eliminates the need for
switching.

8.3 Apparatus

8.3.1 Gas chromatograph

Figure 13 is an example of the layout of an instrument that has been used and found
acceptable. Injection arrangements shall suit the method by which gas is transferred from gas
extraction equipment into the chromatograph.

Thus, the vacuum extraction equipment described in Figure 6 and used for both Toepler pump
and partial degassing methods transfers the gas via a gas sample valve and calibrated
sample loop, a method recommended to improve repeatability.
BS EN 60567:2011
60567 © IEC:2011 – 43 –

Alternatively, gas samples may be transferred and injected into the chromatograph using a
precision gas-tight syringe, and this latter method is generally used for gas samples from gas-
collecting relays.

In the case of extraction by stripping (see Figure 9), a sampling valve is used, with the
stripper inserted in place of the sample loop as shown in Figure 9a. Arrangements where a
stripper plus cold trap are used are shown in Figure 9b.

In the case of the headspace method, the headspace accessories described in 7.5.3.2, a
bypass valve, and a zero-dead volume adapter (0,53 mm ID) for the column connections are
used for injecting extracted gases.

IEC 2469/11

Key
Position A: Sample loop filling Position B: Injection
1 stopcock 8 integrator
2 chromatograph gas sample valve 9 optional restriction valve for pressure
3 sample loop compensation
4 column selector valve 10 switch
5 columns a) column 1 11 methanator
b) column 2 12 H 2 for catalysis
A inlet carrier gas
6 detectors a) thermal conductivity B outlet carrier gas (to GC)
b) flame ionization C injection of gas sample
7 recorder V connection to vacuum
Figure 13 – Schematic arrangement for gas chromatography
 BS EN 60567:2011
– 44 – 60567 © IEC:2011

8.3.2 Columns

In the present examples of Table 4, two columns are used with a two-way valve enabling
selection between the columns.

However, the important requirement for all columns is that they should achieve good
separation in as short a time as possible, while giving all elutions on a stable baseline. The
columns indicated in Table 4 are given only by way of examples and other columns meeting
these general requirements may be used.

In the case of the headspace method, the packed columns described in example 1 of Table 4
can be used for the routine analysis of oils; however, at low gas-in-oil concentration levels,
gases shall be detected in the headspace phase at the nl/l level. This requires the use of the
PLOT columns of example 2 of Table 4. At these nl/l gas levels, special care should be taken
to prevent contamination and in the control of the GC detectors.

8.3.3 Carrier gas

The carrier gas is, preferably, gas chromatograph grade argon.

8.3.4 Detectors

The gases eluted from the columns are passed over a thermal conductivity detector (TCD)
and a flame ionization detector (FID). A helium ionization detector (HID) can be used instead
of the FID and TCD. The HID is 10 times more sensitive than FID, using helium as a carrier
gas and does not require the use of a methanator.

8.3.5 Methanator

In the present examples, a methanator is fitted at the inlet to the flame ionization detector to
improve the sensitivity with which CO and CO 2 can be detected by converting these gases to
methane.

NOTE The activity of the methanator may be impaired by the presence of sulphur hexafluoride (this gas is
sometimes used in cable terminal boxes and may diffuse into the equipment filling oil). In this case, a different
analytical arrangement should be used which is not described in this standard.

The methanator may lose some sensitivity (and the CO 2 /C 2 H 4 and CO/CH 4 ratios decrease) with time, but may be
recalibrated.

8.3.6 Cold trap

When the stripping method is used, a cold trap may be fitted at the outlet of the stripper to
improve the sensitivity for hydrocarbons.

Figure 9b shows an example of the method of inclusion of a cold trap. A typical device used
consists of a 130 mm long, 6 mm OD, stainless steel tube packed with 100/120 mesh Porapak
®
Q or equivalent, maintained below –54 °C in a suitable freezing mixture such as solid
carbon dioxide and alcohol.

During stripping, a separate carrier gas stream circulates in the cold trap while the main
carrier gas flows directly to the gas chromatograph. After stripping, a valve is switched to
direct the carrier gas flow through the cold trap. Then the trap is rapidly heated to 80 °C,
injecting the trapped gases onto the analytical columns.

8.3.7 Integrator and recorder

The electrical outputs from the detectors are fed to an integrator. Additionally or alternatively,
a chart recorder may be used.
BS EN 60567:2011
60567 © IEC:2011 – 45 –

8.4 Preparation of apparatus

a) Set up the chromatograph and allow the flow of carrier gas and the temperature to
stabilize as shown by the production of a steady baseline.
b) For the vacuum extraction methods, either inject the gas sample using a syringe or with
the gas sample loop previously evacuated.
c) For the stripping method, introduce the oil sample into the stripper by means of a precision
syringe.
d) For the headspace method, inject the extracted gases using accessories indicated in
8.3.1.

8.5 Analysis

See Figure 13.

A possible procedure using one chromatograph fitted with two columns, a gas-sampling valve
and a methanator is given below (example 1 of Table 4).

a) Adjust the selector valve (4) (position A) to bring the Porapak ® (5a) or equivalent column
into use.
b) Turn the sample valve (2) to introduce the gas sample.
c) Use the switch (10) to select the flame ionization detector (6b). The first peak to emerge
will be CO converted to CH 4 by the methanator. The second peak will be CH 4 . The third
peak is CO 2 converted to CH 4 by the methanator, and this is followed by C 2 H 4 , C 2 H 6 and
C2H 2.
NOTE The CO and CO 2 , having been converted to CH 4 by the methanator, are detected at high sensitivity by the
flame ionization detector. High concentrations of these gases may well exceed the linear range of this detector. In
this case, use may be made of a thermal conductivity detector to evaluate the CO 2 before methanation.

d) Adjust the selector valve (4) (position B) to bring the molecular sieve column into use.
Obtain a stable baseline.
e) Refill the gas sample loop according to step j) of 7.2.3.
f) Turn the sample valve (2) to introduce the gas sample.
g) Use the switch (10) to select the thermal conductivity detector (6a). Peaks will emerge in
the following order: H 2 , O 2 and N 2 .
h) Use the switch (10) to select the flame ionization detector (6b). The next peak will be
CH 4 ; the last peak to emerge will be CO converted to CH 4 by the methanator.
i) Purge any retained gases from both columns.
j) One determination per gas sample is normally sufficient.

8.6 Calibration of the chromatograph

Retention times are established by injection of dilutions of individual gases in the carrier gas
into the columns. The response factors of the detectors, however, are preferably determined
using a standard gas mixture diluted with the carrier gas, containing known concentrations of
all gas components to be determined, in proportions resembling those found in oils from
transformers. Such a standard mixture should be used periodically, depending upon the
stability of the equipment. For better precision, calibration should be undertaken immediately
before analysis of the oil sample.

The minimum number of standard gas mixtures needed for calibration of the chromatograph
varies from 1 to 3. Only one is needed when performance of analysis equipment has been
found linear (by verification of the entire system) in the concentration range of gases usually
found in transformer oil.

A different standard for verification of GC detectors should be run at least once a day.
 BS EN 60567:2011
– 46 – 60567 © IEC:2011

8.7 Calculations

a) Identify the gas corresponding to each peak by comparison with the chromatograms
obtained during calibration.
b) Measure the area or height of each peak, note its retention time and apply the calibration
data to obtain the gas volumes.
c) When dealing with analyses of gases taken from gas collecting relays, calculate the
concentration of each gas in per cent by volume.
d) When dealing with analyses of gases extracted from oil, calculate the concentration in
microlitres of each gas per litre of the oil from which it was extracted (or micromole of
each gas per litre of oil).

Dissolved gas concentrations in the oil sample CL0 should be converted to these standard
conditions (101,325 kPa and 20 °C), using the following equation:

CL0 (corrected) = CL0 × (P 101,325) × (293 (273 + t ))

where

CL0 is the concentration of gases in the oil sample at ambient temperature and pressure;

t is the ambient temperature, in °C;

P is the atmospheric pressure, in kPa.

NOTE 1 1 µl/ l corresponds to 1 ppm by volume and 0,042 µmol/l at 20 °C and 101,3 kPa.

NOTE 2 Concentrations in µmol/l can be converted to µl/l or ppm, under these standard conditions, by multiplying
by 22,4 (293/273).

NOTE 3 The total gas content of oil by volume, expressed as a percentage, in the case of partial degassing,
stripping and headspace methods, can be estimated by the sum of the individual gas concentrations expressed in
µl/l under these standard conditions.

9 Quality control

9.1 Verification of the entire analytical system

The preferred method of ensuring that the entire system (extraction and chromatography)
gives stable and accurate results is by analysing a known quantity of gas-in-oil standards
(containing all the gases listed in 8.1 in proportions resembling those found in oils taken from
transformers) in place of an oil sample and carrying out all the procedures detailed above.

In the case of the Toepler pump extraction method, it has been confirmed that the extraction
efficiency and performance of the whole analysis equipment can be verified by the daily
analysis of an air-saturated oil standard (see Annex C) and one standard gas mixture with
average gas concentrations in the range usually found in transformer oil samples.

It is recommended to use at least two gas-in-oil standards, one containing low concentrations
of gases (resembling oils in factory tests) and the other containing higher concentrations
(resembling oils from equipment in the field) to check the quality of the results produced by
the analytical system in the entire linearity range. The chromatogram peak areas or heights
can then be related directly to the quantities of gases present in the oil, compensating
automatically for incomplete extraction and other operational factors.

It is good practice to repeat this procedure at intervals of calibration of not more than six
months or following changes in apparatus or operating conditions.
BS EN 60567:2011
60567 © IEC:2011 – 47 –

9.2 Limits of detection and quantification

The basic requirement is that the analytical system, consisting of degassing equipment and
gas chromatograph, shall have adequate sensitivity for the task for which it is designed.

Not only the detection limit, but also the sensitivity, the repeatability and the accuracy of
results depend on many details of the overall procedure, in particular the method of extraction
and the design and method of operation of the gas chromatograph and its ancillaries.

For example, by using a methanator combined with a flame ionization detector, instead of
using a thermal conductivity detector, the sensitivity and detection limit for the carbon oxides
are considerably improved.

Tests on equipment in service where the dissolved gas concentration is often high do not
require the same detection limits as factory tests where gas concentrations are usually very
low.

In the case of headspace, extraction efficiency is low, and the concentration of gases in the
extracted gas phase typically 100 times lower than with the other extraction methods. At low
gas-in-oil concentration levels, detection limits in the nl/l range in the gas phase of the
headspace are therefore necessary, requiring the use of more sensitive equipment and
procedures (see 7.5.4.3).

It is necessary that each laboratory determines overall procedures that will give suitable
sensitivities for all gases. For guidance, experience indicates that the entire analytical system
should be capable of detecting gases dissolved in oil at the concentrations indicated in
Table 5.

For the analysis of gas samples taken from gas-collecting relays, a detection limit equivalent
to that obtained for the analyses of gases extracted from the oil for service tests is adequate.

NOTE The limit of detection is defined as the lowest concentration that can be identified. The limit of
quantification is defined as the lowest concentration that can be quantified with a reasonable precision and
accuracy.

Table 5 – Required limits of detection in oil

Acceptance tests Service tests

Gases Concentrations at 20 °C

µl/l µmol/l µl/l µmol/l

Hydrogen 2 0,08 5 0,2
Hydrocarbons 0,1 0,004 1 0,042
Carbon monoxide 5,0 0,2 25 1,0
Carbon dioxide 10 0,4 25 1,0
Oxygen 500 21 500 21
Nitrogen 2 000 84 2 000 84

9.3 Repeatability, reproducibility and accuracy

9.3.1 General remark

Repeatability (r), reproducibility (R) and accuracy are defined in detail in ISO 5725.
 BS EN 60567:2011
– 48 – 60567 © IEC:2011

9.3.2 Repeatability

Repeatability is related to the differences that are observed when the same oil sample is
analysed several times by the same laboratory over the same day or a short period of time.

Having established methods that give adequate overall detection limits, each laboratory shall
confirm that these methods give adequate repeatability following the procedure described in
ISO 5725.

For gas concentration levels greater than 10 µl/l the repeatability of a laboratory shall be
considered as acceptable if the absolute difference (A – B) of two measurements A and B
satisfies the following equation:

r = (A – B) < k × (A + B) /2

which means that the repeatability of the laboratory, at 95 % confidence limit, is lower than k
times the mean concentration of the gas analysed. The k coefficient depends on the nature of
the gas analysed.

A general acceptable value, calculated from an international IEC inter-laboratory test is:
k = 0,07 for concentrations > 10 µl/l and < 1 000 µl/l, and k = 0,10 for concentrations
>1 000 µl/l.

For low gas concentrations (for example, < 10 µl/l), the required repeatability is given by the
following equation: r = S (where S = detection limit), whatever the concentration, as deduced
from the same international IEC inter-laboratory test.

It is recommended that each laboratory check its own individual repeatability at both
concentration levels at appropriate time intervals or after major changes on its system (gas
extractor and gas chromatograph). To do that, a sufficient number of analyses on multiple
samples of the same oil are run within a short period of time (less than one day), then the
repeatability of results r is determined according to ISO 5725.

9.3.3 Reproducibility

Reproducibility is related to the differences which are observed when the same oil sample is
analysed by different laboratories (inter-laboratory reproducibility), or when it is analysed by
the same laboratory over long periods of time (after several days, weeks or months) (intra-
laboratory reproducibility).

Inter-laboratory reproducibility has been evaluated by CIGRE as around ± 20 % at medium

concentration levels.

It is recommended that each laboratory check its own intra-laboratory reproducibility at

different concentration levels at appropriate time intervals or after major changes on its
system (gas extractor and gas chromatograph). To do that, analyse multiple samples of the
same oil at regular intervals of time, for instance each week or each month over a period of
several months, then determine the reproducibility of results R according to ISO 5725.

A good conservation of the samples is necessary between analyses. Storing the samples in a
fridge is recommended to avoid reactions with light and oxygen present in the oil.

9.3.4 Accuracy

Accuracy is related to the differences that are observed between the values analysed by a
laboratory and the true values of dissolved gases contained in the oil sample.
BS EN 60567:2011
60567 © IEC:2011 – 49 –

Inaccurate DGA results may lead to wrong fault diagnoses, especially if gas ratios are close
to a fault zone boundary, or to inappropriate actions on the equipment, if concentration values
are close to the typical or alarm values defined in IEC 60599.

To be able to determine accuracy the nominal values of dissolved gas concentrations have to
be known. The mean of several measured values has been shown by inter-laboratory tests to
be different from the nominal values. Determination of accuracy shall be carried out with gas-
in-oil standards prepared according to Clause 6, or through participation to round robin tests
using such standards, or with certified gas-in-oil standards prepared according to ISO 5725.

Examples of accuracies that can be obtained using the overall experimental procedure are
given in Table 6. These values are deduced from IEC and CIGRE inter-laboratory tests made
on two gas-in-oil standards (prepared according to 6.2) and involving 44 laboratories
worldwide. One standard sample contained medium gas concentration levels (hydrocarbons
between 9 µl/l and 60 µl/l, CO and CO 2 between 100 µl/l and 500 µl/l). The other one
contained low gas concentration levels (hydrocarbons between 1 µl/l and 10 µl/l, CO and CO 2
between 30 µl/l and 100 µl/l).

It is recommended that each laboratory determines its own accuracy, which may differ from
the values in Table 6. To do that, analyse a gas-in-oil standard according to Clause 6, then
determine the accuracy according to ISO 5725.

Table 6 – Examples of accuracy of extraction methods

Accuracy, in percentage of the nominal value

Extraction procedure Medium concentration Low concentration
Toepler 13 35
Partial degassing 13 30
Stripping 18 23
Headspace 18 37

Mercury-free Toepler 15 a 14 a
Mercury-free partial degassing 11 a
Shake test 15 44
a Based on a limited number of analyses.

10 Report of results

The report for DGA shall include

– a reference to this standard;

– information on the gas or oil sample (see Clause 4 of this standard or 4.4 of
IEC 60475:2011, respectively);
– the sampling procedure used (for example, syringe, bottle) (see Clause 3 of this standard
and Clause 4 of IEC 60475:2011, respectively);
• the extraction procedure used (for example, Toepler, headspace) (see Clause 7 and
Annex B);
• for headspace analysis, reference for the Ostwald coefficients used in case of
calibration with gas standards (see 7.5.5.3);
– the detection limits for each gas with the analysis procedure used (see 9.2);
– for each gas analysed, the results in µl/l or in µmoles/l (see 8.7).
 BS EN 60567:2011
– 50 – 60567 © IEC:2011

NOTE 1 When available, it may be useful for diagnosis purposes to indicate the average accuracies obtained by
the laboratory at these gas levels with the analysis procedure used (see 9.3.4).

NOTE 2 Guidelines for drafting the report in terms of quality assurance can be found in ISO/IEC 17025.
BS EN 60567:2011
60567 © IEC:2011 – 51 –

Annex A
(informative)

Correction for incomplete gas extraction

in partial degassing method by calculation

From the chromatogram, the sample oil volume, the calculated total volume of gas extracted
and the volume of the aliquot of gas passed into the chromatograph, determine the apparent
volume concentration C i of each component gas extracted from the oil.

Calculate the equilibrium extraction efficiency for each component gas from

Ei = 1 (1 + ai V0 Vt )

where
Ei is the extraction efficiency for component i;
V0 is the volume of the oil sample, in ml;
Vt is the total expansion volume, in ml (see 7.3.3);
ai is the Ostwald solubility coefficient of component i.

Examples of solubility coefficients for typical mineral oils are shown in Table A.1.

Table A.1 – Examples of solubility coefficients a i (at 25 ºC)

reported by CIGRE TF D1.01.15

Gas Mineral oils Natural esters Synthetic esters Silicone oils

Hydrogen 0,055 6 0,047 0 0,051 0 0,092 4
Nitrogen 0,090 7 0,072 8 0,087 2 0,157
Carbon 0,132 0,111 0,127 0,204
monoxide
Oxygen 0,172 0,134 0,152 0,266
Methane 0,429 0,341 0,381 0,569
Carbon dioxide 1,09 1,54 2,05 1,63
Acetylene 1,24 2,68 4,38 2,04
Ethylene 1,84 1,69 1,87 2,18
Ethane 2,82 2,16 2,19 3,10

The data given in Table A.1 represent mean values obtained by bubbling the pure gases in
some of the current types of transformer oils. The actual data on specific types of oils may
differ a little from these figures.

The data given in the above table represent mean values obtained on some of the current
types of transformer oils. The actual data may differ a little from these figures.

Calculate the corrected volume concentration of each gas in the oil from:

C i (corrected) = C i (apparent)/E i

NOTE 1 Solubility coefficients are functions of temperature and of oil density.

NOTE 2 Instead of correcting for incomplete gas extraction by calculation, calibration of the partial degassing
method with several gas-in-oil standards at different concentration levels may be used.
 BS EN 60567:2011
– 52 – 60567 © IEC:2011

NOTE 3 When using the partial degassing method, the measurement of total gas content may need to be
corrected (by a factor of up to 60 %) in order to take into account the vapour pressure of water, which depends on
the water content in oil.
BS EN 60567:2011
60567 © IEC:2011 – 53 –

Annex B
(informative)

Mercury-free and shake test versions of the standard extraction methods

A mercury-free version of the Toepler method is available commercially. In this equipment,

mechanical pistons are used instead of the mercury piston to extract the dissolved gases and
recompress them.

A typical schematic representation of this equipment is indicated in Figure B.1a. Some

versions can be automated with an oil sample carousel so that large numbers of samples can
be injected and analysed on a 24 h basis with unattended operation.

A mercury-free version of the partial degassing method is available commercially. In this

equipment, mechanical pistons are used instead of the mercury piston to extract the dissolved
gases and recompress them.

A typical schematic representation of this equipment is indicated in Figure B.1b.

A simplified version of the headspace method is available commercially (the so-called “shake-
test” method). In this version, an oil sample (90 ml) is introduced in a 100 ml precision glass
syringe rather than in a glass vial. 10 ml of air are then introduced in the syringe. The syringe
is shaken vigorously by hand to extract the dissolved gases. Equilibrium is reached in less
than 2 min because of the high shaking efficiency. An aliquot of the extracted gases is then
injected in a portable chromatograph for on-site analysis, or in a standard laboratory
chromatograph. A typical schematic representation of this equipment is indicated in
Figure B.1d.

Examples of accuracies that can be obtained using these methods are given in Table 6.

These values are deduced from inter-laboratory tests made on two gas-in-oil standards
prepared as in 9.3 and involving 10 laboratories world wide (2 for mercury-free Toepler, 1 for
mercury-free partial degassing, and 7 for the shake test).
 BS EN 60567:2011
– 54 – 60567 © IEC:2011

2 2

5
1 7
10 9

3 6 3 6
4

8 7
5
4

5 IEC 2470/11

11 1 8
IEC 2470/11

Key Key
1 vacuum pump 1 vacuum pump
2 oil inlet 2 oil inlet
3 oil sample 3 gas extraction chamber (glass)
4 gas extraction chamber 4 oil sample
5 piston 5 pressure gauge
6 gas compression chamber 6 gas compression chamber (glass)
7 to GC injection loop and detectors 7 piston
8 oil purge 8 atmospheric air
9 to GC injection loop and detectors
10 calibration gas
11 oil purge
Figure B.1a – Mercury-free Toepler Figure B.1b – Mercury-free partial degassing

3
6
6
5
8
7 7
1 5
2

3
2
IEC 2473/11
1
IEC 2472/11

Key Key
1 vial 1 precision syringe
2 septum 2 piston
3 oil sample 3 oil/air inlet
4 gas phase (Ar or He) 4 oil sample
5 carrier gas (Ar or He) 5 gas phase (air)
6 pressurization gauge 6 to GC injection loop and detectors
7 needle
8 to GC injection loop and detectors
Figure B.1c – Headspace Figure B.1d – Shake test

Figure B.1 – Schematic representation of methods in Annex B

BS EN 60567:2011
60567 © IEC:2011 – 55 –

Annex C
(informative)

Preparation of air-saturated standards

Keep a batch of new transformer mineral or non-mineral oil in an open container at room
temperature for at least one week. Measure the oxygen and nitrogen content in the oil, using
any one of the gas extraction methods, then the air content of the oil at saturation.

The gas extraction equipment is checked with this air-saturated oil standard (see 9.1) and
found correct if the average total gas content measured corresponds to the value measured
for this type of oil, with a standard deviation of 3 %.

The gas extractor and the gas chromatograph are checked by the retention times and
concentrations of O 2 , N 2 and CO 2 in this air-saturated oil standard. All three retention times
should be in accordance with those obtained with gas standard mixtures.

The solubility of air in oil at saturation depends on atmospheric pressure and temperature and
on the type of oil used. Examples of solubility values of air for different types of oils, as
reported by CIGRE TF D1.01.15, are indicated in Table C.1.

Table C.1 – Examples of solubility values of air for different oil types

Fluid Density µl/l at 20 °C

at 20 °C
O2 N2 CO 2 Air
Mineral oil 1 0,851 8 29 980 65 320 569 95 869
Mineral oil 2 0,888 2 32 080 61 780 537 94 397
Natural ester 1 0,921 0 21 995 49 613 647 72 255
Natural ester 2 0,915 8 24 507 50 177 625 75 309
Synthetic ester 0,919 7 21 705 45 269 555 67 529
Silicone oil 0,964 5 54 938 113 078 763 168 779

Examples of variations with temperature of the solubility of oxygen and nitrogen in a mineral
oil as reported by CIGRE TF D1.01.15 are given in Table C.2.

Table C.2 – Examples of temperature variations for oxygen

and nitrogen solubility in mineral oil

Temperature O2 N2
°C
13 32 937 62 798
21,5 32 750 63 728
25 32 483 64 061
50 31 465 66 141
 BS EN 60567:2011
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Annex D
(informative)

Correction for gas bubbles in syringes and air gap in rigid bottles

It has been found by CIGRE TF D1.01.15 that gas bubbles are observed in oil in about 20 %
of syringes on average (this value may be lower or higher depending on the experience of
samplers).

When using the Toepler, partial degassing and stripping methods, the bubble is introduced
into the extraction vessel (see 7.2.3, point e), NOTE 1), and no correction is necessary. When
using the headspace method, the bubble should not be introduced in the vial, and a correction
for the gases having migrated into the bubble should be made.

In glass or rigid metal bottles, the air gap volume used as an oil expansion device is about
2 ml to 5 ml depending on the size of the bottle (1 l or 2 l). A correction for the gases having
migrated into the air gap should also be made.

The following equation can be used for that purpose, for each gas measured:

C C = C m (1 + V G / (kV L +V G ))

where
CC is the corrected concentration, in µl/l;
Cm is the measured concentration, in µl/l;
VG is the volume of bubble in the syringe, or volume of air gap in the glass bottle, in ml;
VL is the volume of oil in the syringe or glass bottle, in ml;
k is the Ostwald (solubility) coefficient.
NOTE In general, the corrections to be made (10 % to 5 %) are significant only for the less soluble gases (H 2 ,
CO).
BS EN 60567:2011
60567 © IEC:2011 – 57 –

Annex E
(informative)

Procedure for comparing gas monitor readings to laboratory results

Gas monitors (installed on-line on electrical equipment in service or used as portable

instruments) are increasingly used in industry. In some cases, monitors readings do not quite
agree with laboratory results for the same equipment, and it is not possible to know for sure
which is right, monitors readings or laboratory results.

The following procedure has been developed by CIGRE TF15 to make such an evaluation
(see CIGRE TB 409).

– Purchase a sample of gas-in-oil standard from an appropriate vendor, or prepare one

according to IEC 60567 (this standard) or ASTM D3612.
– Take a reading on one or several on-line gas monitors installed on transformers in service.
– Take 4 duplicate samples of oil from the sampling point of the monitor(s), immediately
after having taken the reading.
– For portable gas monitors, take 5 duplicate samples of oil from a transformer. Using one
of the 5 samples, take a reading of the portable monitor.
– Send all the above samples of oil to the DGA laboratory.
– Analyse all samples on the same day (or over no more than a few days), using the same
analytical equipment for all samples.
– Convert all DGA results and monitor readings to the same units (IEC or STP µl/l).
– Calculate the bias of the laboratory by comparing its results for the gas-in-oil standard
sample to what was actually prepared.
– Correct all other DGA lab results using the bias calculated above.
– Calculate the average values (A) of each set of 4 duplicate samples, in µl/l.
– Calculate the repeatability (R) of laboratory results as the difference between results for
the individual 4 samples and average values (A), and express it as a percentage.
– Calculate the difference (D) between gas monitor readings and average values (A), and
express it as a percentage.
– The maximum accuracy of the gas monitor as measured by the laboratory is (D – R – 2),
in per cent, where 2 % is the uncertainty on the gas-in-oil standard.

For example, if

– gas-in-oil standard S = 100 µl/l, laboratory result for S = 90 µl/l,

– laboratory results for 4 duplicate samples = 250, 230, 210, 240 µl/l,
– laboratory results corrected for bias = 275, 253, 231, 264 µl/l,
– average value (A) = 256 µl/l, repeatability (R) = 9 %,
– monitor reading = 300 µl/l, difference (D) = +17 %,
– maximum accuracy of gas monitor = (17 – 9 – 2) = +6 %.
 BS EN 60567:2011
– 58 – 60567 © IEC:2011

Bibliography

[1] ISO/IEC 17025, General requirements for the competence of testing and calibration
laboratories

[2] ISO 3675, Crude petroleum and liquid petroleum products – Laboratory determination
of density – Hydrometer method

[3] CIGRE Technical Brochure 409, Report on gas monitors for oil-filled electrical
equipment, 2010

[4] CIGRE Technical Brochure 443, Report on DGA in non-mineral oils and load tap
changers and improved DGA diagnosis criteria, Electra 253, December 2010

[5] ASTM D3612, Standard Test Method for Analysis of Gases Dissolved in Electrical
Insulating Oil by Gas Chromatography

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