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IEC TR 63025
®
Edition 1.0 2021-07

TECHNICAL
REPORT

colour
inside

Insulating liquids – Quantitative determination of methanol and ethanol in

insulating liquids

INTERNATIONAL
ELECTROTECHNICAL
COMMISSION

ICS 29.040.10 ISBN 978-2-8322-9990-6

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® Registered trademark of the International Electrotechnical Commission

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CONTENTS
FOREWORD ........................................................................................................................... 4
INTRODUCTION ..................................................................................................................... 6
1 Scope .............................................................................................................................. 8
2 Normative references ...................................................................................................... 8
3 Terms and definitions ...................................................................................................... 8
4 Symbols and abbreviated terms ....................................................................................... 9
5 Sampling ....................................................................................................................... 10
6 Principle of the methods ................................................................................................ 10
7 Method A – HS-GC-MS .................................................................................................. 10
7.1 General ................................................................................................................. 10
7.2 Apparatus ............................................................................................................. 10
7.2.1 Analytical balance ......................................................................................... 10
7.2.2 Headspace sampler ....................................................................................... 10
7.2.3 Gas chromatograph coupled with mass spectrometry detector ....................... 11
7.3 Reagents and materials ........................................................................................ 11
7.3.1 Laboratory equipment and glassware ............................................................. 11
7.3.2 Standard chemicals ....................................................................................... 11
7.3.3 GC carrier gases ........................................................................................... 12
7.4 Preparation of standard solutions .......................................................................... 12
7.4.1 General ......................................................................................................... 12
7.4.2 Degassed insulating liquid ............................................................................. 12
7.4.3 Internal standard stock solution ..................................................................... 12
7.4.4 Standard solutions of methanol and ethanol .................................................. 13
7.5 Sample preparation ............................................................................................... 14
7.6 Headspace sampler parameters ............................................................................ 15
7.7 Gas chromatograph parameters ............................................................................ 15
7.7.1 Injector .......................................................................................................... 15
7.7.2 Carrier gas .................................................................................................... 15
7.7.3 Temperature ramp ......................................................................................... 15
7.8 Mass spectrometer parameters ............................................................................. 16
7.9 Analysis procedure ............................................................................................... 16
7.10 Internal standard calibration .................................................................................. 17
7.10.1 General ......................................................................................................... 17
7.10.2 Response factor determination ...................................................................... 18
7.11 Expression of the results ....................................................................................... 18
8 Method B – HS-GC-FID ................................................................................................. 18
8.1 General ................................................................................................................. 18
8.2 Apparatus ............................................................................................................. 18
8.2.1 Analytical balance ......................................................................................... 18
8.2.2 Headspace sampler ....................................................................................... 18
8.2.3 Gas chromatograph with flame ionization detector ......................................... 19
8.3 Reagents and materials ........................................................................................ 19
8.3.1 Laboratory equipment and glassware ............................................................. 19
8.3.2 Standard chemicals ....................................................................................... 19
8.3.3 GC carrier gases ........................................................................................... 19
8.4 Preparation of standard solutions .......................................................................... 20
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8.4.1 General ......................................................................................................... 20

8.4.2 Degassed insulating liquid ............................................................................. 20
8.4.3 Standard solutions of methanol and ethanol .................................................. 20
8.5 Sample preparation ............................................................................................... 21
8.6 Headspace sampler parameters ............................................................................ 21
8.7 Gas chromatograph parameters ............................................................................ 22
8.7.1 Injector .......................................................................................................... 22
8.7.2 Carrier gas .................................................................................................... 22
8.7.3 Temperature ramp ......................................................................................... 22
8.7.4 FID parameters .............................................................................................. 22
8.8 Analysis procedure ............................................................................................... 22
8.9 Calibration ............................................................................................................ 23
8.10 Expression of the results ....................................................................................... 23
9 Test report ..................................................................................................................... 23
10 Precision ....................................................................................................................... 24
10.1 Verification of the entire analytical system ............................................................ 24
10.2 General ................................................................................................................. 24
10.3 Detection limits of Method A and Method B ........................................................... 24
10.4 Repeatability ......................................................................................................... 24
10.5 Reproducibility ...................................................................................................... 25
Bibliography .......................................................................................................................... 26

Figure 1 – Comparison of methanol and 2-furfural production in mineral oil versus

cellulose scission number ....................................................................................................... 7
Figure 2 –Typical chromatogram with selected ion (m/z = 31) mass spectrum ....................... 17
Figure 3 – Typical GC-FID chromatogram ............................................................................. 23

Table 1 –Method A – Example of GC temperature ramp parameters ..................................... 16

Table 2 – Method A – m/z values of internal standard ions .................................................... 16
Table 3 – Method B – Examples of FID parameters reported in literature .............................. 22
Table 4 – Detection limits of Method A and Method B, in mineral oil ..................................... 24
Table 5 – Repeatability (r) in % for Method A (HS-GC-MS), in mineral oil ............................. 24
Table 6 – Reproducibility (R) in % for Method A (HS-GC-MS), in mineral oil .......................... 25
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INTERNATIONAL ELECTROTECHNICAL COMMISSION

____________

INSULATING LIQUIDS – QUANTITATIVE DETERMINATION OF

METHANOL AND ETHANOL IN INSULATING LIQUIDS

FOREWORD
1) The International Electrotechnical Commission (IEC) is a worldwide organization for standardization comprising
all national electrotechnical committees (IEC National Committees). The object of IEC is to promote international
co-operation on all questions concerning standardization in the electrical and electronic fields. To this end and
in addition to other activities, IEC publishes International Standards, Technical Specifications, Technical Reports,
Publicly Available Specifications (PAS) and Guides (hereafter referred to as “IEC Publication(s)”). Their
preparation is entrusted to technical committees; any IEC National Committee interested in the subject dealt with
may participate in this preparatory work. International, governmental and non-governmental organizations liaising
with the IEC also participate in this preparation. IEC collaborates closely with the International Organization for
Standardization (ISO) in accordance with conditions determined by agreement between the two organizations.
2) The formal decisions or agreements of IEC on technical matters express, as nearly as possible, an international
consensus of opinion on the relevant subjects since each technical committee has representation from all
interested IEC National Committees.
3) IEC Publications have the form of recommendations for international use and are accepted by IEC National
Committees in that sense. While all reasonable efforts are made to ensure that the technical content of IEC
Publications is accurate, IEC cannot be held responsible for the way in which they are used or for any
misinterpretation by any end user.
4) In order to promote international uniformity, IEC National Committees undertake to apply IEC Publications
transparently to the maximum extent possible in their national and regional publications. Any divergence between
any IEC Publication and the corresponding national or regional publication shall be clearly indicated in the latter.
5) IEC itself does not provide any attestation of conformity. Independent certification bodies provide conformity
assessment services and, in some areas, access to IEC marks of conformity. IEC is not responsible for any
services carried out by independent certification bodies.
6) All users should ensure that they have the latest edition of this publication.
7) No liability shall attach to IEC or its directors, employees, servants or agents including individual experts and
members of its technical committees and IEC National Committees for any personal injury, property damage or
other damage of any nature whatsoever, whether direct or indirect, or for costs (including legal fees) and
expenses arising out of the publication, use of, or reliance upon, this IEC Publication or any other IEC
Publications.
8) Attention is drawn to the Normative references cited in this publication. Use of the referenced publications is
indispensable for the correct application of this publication.
9) Attention is drawn to the possibility that some of the elements of this IEC Publication may be the subject of patent
rights. IEC shall not be held responsible for identifying any or all such patent rights.

IEC TR 63025 has been prepared by IEC technical committee 10: Fluids for electrotechnical
applications. It is a Technical Report.

The text of this Technical Report is based on the following documents:

Draft Report on voting

10/1112/DTR 10/1131/RVDTR

Full information on the voting for its approval can be found in the report on voting indicated in
the above table.

The language used for the development of this Technical Report is English.

This document was drafted in accordance with ISO/IEC Directives, Part 2, and developed in
accordance with ISO/IEC Directives, Part 1 and ISO/IEC Directives, IEC Supplement, available
at www.iec.ch/members_experts/refdocs. The main document types developed by IEC are
described in greater detail at www.iec.ch/standardsdev/publications.
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IEC TR 63025:2021 © IEC 2021 –5–

The committee has decided that the contents of this document will remain unchanged until the
stability date indicated on the IEC website under webstore.iec.ch in the data related to the
specific document. At this date, the document will be

• reconfirmed,
• withdrawn,
• replaced by a revised edition, or
• amended.

IMPORTANT – The "colour inside" logo on the cover page of this document indicates
that it contains colours which are considered to be useful for the correct understanding
of its contents. Users should therefore print this document using a colour printer.
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INTRODUCTION

It has been demonstrated over several years that the ageing of impregnated paper in insulating
liquid, which results in cellulose degradation, produces molecules of light alcohols, methanol
(MeOH) and ethanol (EtOH). In laboratory experiments, a good correlation has been established
between the increase of the methanol content in insulating liquid and the decrease of the degree
of polymerization of the cellulose, irrespective of the type of paper, standard kraft or thermally
upgraded. Further, at the early stages of paper ageing, i.e. of cellulose degradation, the
methanol content is always higher than that of furanic compounds (mainly 2-furfural), so this
behaviour suggests that methanol could be a relevant in-oil marker to detect early paper ageing
in transformers and to assess its evolution (see Figure 1).

Ethanol is a second light alcohol of interest that these methods would be able to detect.

It should be emphasized that in a real transformer the situation is much more complicated than
in laboratory setups, so the relationship between in situ paper degradation and tracer
concentration (MeOH, EtOH, as well as 2-FAL) is much more complex and hard to establish.

In order to address the growing interest of industry in using these alcohols as tracers of
cellulosic material ageing in operating equipment, there is a need for the development of a
document describing analytical methods to quantify methanol and ethanol in the different types
of insulating liquids. The objective is for one of these methods to remain as simple and
affordable as possible, and for the other to be more sophisticated and more accurate.

The principle of this Technical Report was brought up and discussed during the IEC TC 10
plenary meeting held in Vienna in November 2013. A project team was set up to prepare test
methods for the unambiguous quantitative determination of methanol and ethanol in unused
and used insulating liquids.

WARNING – Health and safety

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

The insulating liquids which are the subject of this document should be handled with due regard
to personal hygiene. Direct contact with eyes may cause slight 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 document involve the use of processes that could lead to a
hazardous situation. Attention is drawn to the relevant standard for guidance.

WARNING – Environment

This document involves mineral oils, ester liquids, chemicals and used sample containers. The
disposal of these items should be carried out in accordance with current national legislation
with regard to their impacts on the environment. Every precaution should be taken to prevent
the release into the environment of the chemicals used during the test.
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IEC TR 63025:2021 © IEC 2021 –7–

a) Clupak HD75 specimens

b) Manning 220 mannitherm D specimens

Key

NS: number of scissions, inversely proportional to the polymerization degree (DPv)

a): standard kraft paper

b): thermally upgraded paper

NOTE See Jalbert J., Gilbert R., Tétreault P., Morin B. and Lessard-Déziel D. (2007) in the Bibliography.

Figure 1 – Comparison of methanol and 2-furfural production in mineral oil

versus cellulose scission number
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INSULATING LIQUIDS – QUANTITATIVE DETERMINATION OF

METHANOL AND ETHANOL IN INSULATING LIQUIDS

1 Scope

This document specifies two test methods for methanol and ethanol determination in insulating
liquids.

Methanol (MeOH) and ethanol (EtOH) are two light alcohols generated during the degradation
process of cellulosic materials. They are soluble in insulating liquids so they can be regarded
as ageing tracers whose concentrations in oil reflect the degradation of insulating cellulosic
materials in liquid-impregnated transformers.

2 Normative references

There are no normative references in this document.

3 Terms and definitions

For the purposes of this document, the following terms and definitions apply.

ISO and IEC maintain terminological databases for use in standardization at the following
addresses:

• IEC Electropedia: available at http://www.electropedia.org/

• ISO Online browsing platform: available at http://www.iso.org/obp

3.1
flame ionization detector
device in which hydrocarbons are burned in a hydrogen-air flame and the electrical current
caused by the resulting ions is measured between two electrodes

Note 1 to entry: The flame ionization detector is used in gas chromatography mainly to detect hydrocarbon
compounds.

[SOURCE: ISO 14532:2014, 2.4.8, modified – "detector" replaced with "device".]

3.2
gas chromatograph
GC
device used to determine complex mixture components that can be vaporized without
decomposition then separated by differential migration with a carrier gas through a stationary
phase in a column

Note 1 to entry: The method used is called "gas chromatography" (GC).

[SOURCE: IEC 62697-1:2012, 3.1.14, modified – "used for separating volatile and semi-volatile
compounds in mixtures" replaced with "used to determine complex mixture components",
"through differential migration" replaced with "then separated by differential migration" and "a
stationary phase" and Note 1 to entry added.]

3.3
headspace extraction
procedure for collecting the volatile compounds emitted by a specimen enclosed in an airtight
vial under controlled conditions