ISO/FDIS 12810
(Main)Fluorocarbon refrigerants — Specifications and test methods
Fluorocarbon refrigerants — Specifications and test methods
ISO 12810:2003 defines the maximum levels of contaminants for various commercially available fluorocarbon refrigerants and blends containing fluorocarbon refrigerants regardless of their source (new, reclaimed or repackaged). ISO 12810:2003 also establishes test methods for determining the levels of these contaminants. The fluorocarbon refrigerants included in this ISO 12810:2003 are those identified in ANSI/ASHRAE 34 as R 11, R 12, R 13, R 22, R 23, R 32, R 113, R 114, R 123, R 124, R 125, R 134a, R 143a, R 401A, R 401B, R 402A, R 402B, R 500, R 502, and R 503. Only those fluorocarbon refrigerants listed in ANSI/ASHRAE 34 are addressed in ISO 12810:2003.
Fluides frigorigènes fluorocarbonés — Spécifications et méthodes d'essai
General Information
Buy Standard
Standards Content (Sample)
FINAL
INTERNATIONAL ISO/FDIS
DRAFT
STANDARD 12810
ISO/TC 86/SC 8
Fluorocarbon refrigerants —
Secretariat: ANSI
Specifications and test methods
Voting begins on:
2002-12-19
Fluides frigorigènes fluorocarbonés — Spécifications et méthodes
d'essai
Voting terminates on:
2003-02-19
Please see the administrative notes on page iii
RECIPIENTS OF THIS DRAFT ARE INVITED TO
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ING DOCUMENTATION.
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Reference number
BEING ACCEPTABLE FOR INDUSTRIAL, TECHNO-
ISO/FDIS 12810:2002(E)
LOGICAL, COMMERCIAL AND USER PURPOSES,
DRAFT INTERNATIONAL STANDARDS MAY ON
OCCASION HAVE TO BE CONSIDERED IN THE
LIGHT OF THEIR POTENTIAL TO BECOME STAN-
DARDS TO WHICH REFERENCE MAY BE MADE IN
©
NATIONAL REGULATIONS. ISO 2002
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ISO/FDIS 12810:2002(E)
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ii © ISO 2002 — All rights reserved
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ISO/FDIS 12810:2002(E)
In accordance with the provisions of Council Resolution 15/1993, this document is circulated in the
English language only.
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ISO/FDIS 12810:2002(E)
Contents Page
Foreword .vi
Introduction.vii
1 Scope.1
2 Conformance .1
3 Normative references.1
4 Terms, definitions, symbols and abbreviated terms .1
4.1 Terms and definitions .1
4.2 Symbols and abbreviations.2
5 Characterization of refrigerants and requirements for contaminants .3
6 Principle .6
7 Sampling .6
7.1 Precautions .6
7.2 Procedure.6
8 Procedure.7
8.1 Product hazards .7
8.2 Determination .7
9 Test report.9
Annex A (normative) Determination of non-condensable gas in new and reclaimed refrigerants by
gas chromatography.10
Annex B (normative) Determination of water in new and reclaimed refrigerants by Karl Fischer
coulometric titration.18
Annex C (normative) Determination of purity of new and reclaimed refrigerant 11 by gas
chromatography .23
Annex D (normative) Determination of purity of new and reclaimed refrigerant 12 by gas
chromatography .32
Annex E (normative) Determination of purity of new and reclaimed refrigerant 13 by gas
chromatography .43
Annex F (normative) Determination of purity of new and reclaimed refrigerant 22 by gas
chromatography .52
Annex G (normative) Determination of purity of new and reclaimed refrigerant 23 by gas
chromatography .65
Annex H (normative) Determination of purity of new and reclaimed refrigerant 32 by gas
chromatography .74
Annex I (normative) Determination of purity of new and reclaimed refrigerant 113 by gas
chromatography .86
Annex J (normative) Determination of purity of new and reclaimed refrigerant 114 by gas
chromatography .94
Annex K (normative) Determination of purity of new and reclaimed refrigerant 123 by capillary
and packed column gas chromatography .105
Annex L (normative) Determination of purity of new and reclaimed refrigerant 124 by gas
chromatography .116
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ISO/FDIS 12810:2002(E)
Annex M (normative) Determination of purity of new and reclaimed refrigerant 125 by gas
chromatography. 127
Annex N (normative) Determination of purity of new and reclaimed refrigerant 134a by gas
chromatography. 138
Annex O (normative) Determination of purity of new and reclaimed refrigerant 143a by gas
chromatography. 152
Annex P (normative) Determination of composition of new and reclaimed refrigerant 401 blends
of R 22, R 152a and R 124 by gas chromatography . 164
Annex Q (normative) Determination of composition of new and reclaimed refrigerant 402 blends
of R 125, R 22 and R 290 by gas chromatography . 171
Annex R (normative) Determination of azeotropic composition of new and reclaimed refrigerant
500 by gas chromatography . 178
Annex S (normative) Determination of azeotropic composition of new and reclaimed refrigerant
502 by gas chromatography . 185
Annex T (normative) Determination of azeotropic composition of new and reclaimed refrigerant
503 by gas chromatography . 192
Annex U (normative) Determination of high boiling residue in new and reclaimed refrigerants by
volumetric and/or gravimetric measurement and determination of particulate residue by
visual inspection . 198
Annex V (normative) Determination of acidity in new and reclaimed refrigerants by titration. 203
Annex W (normative) Determination of chloride in new and reclaimed refrigerants by silver
chloride precipitation. 207
Bibliography . 211
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ISO/FDIS 12810:2002(E)
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies
(ISO member bodies). The work of preparing International Standards is normally carried out through ISO
technical committees. Each member body interested in a subject for which a technical committee has been
established has the right to be represented on that committee. International organizations, governmental and
non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the
International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.
International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.
The main task of technical committees is to prepare International Standards. Draft International Standards
adopted by the technical committees are circulated to the member bodies for voting. Publication as an
International Standard requires approval by at least 75 % of the member bodies casting a vote.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. ISO shall not be held responsible for identifying any or all such patent rights.
ISO 12810 was prepared by Technical Committee ISO/TC 86, Refrigeration and air-conditioning,
Subcommittee SC 8, Refrigerants and refrigeration lubricants.
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ISO/FDIS 12810:2002(E)
Introduction
Imperial (English) units (I-P) are used in these annexes to describe certain equipment and apparatus which
are generally described commercially only in Imperial (English) dimensions (inch-pounds).
The lengths and diameters of the packed columns used with the gas chromatograph are given in Imperial
dimensions in most annexes because they are designated commercially in Imperial (English) units. If other
sizes of packed columns are used, differences in the test results will be experienced as the retention times will
change. If other sizes of packed columns are employed, it will be necessary for the user to demonstrate that
they produce results that are equivalent in terms of sensitivity, precision and accuracy to those specified in
this International Standard.
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FINAL DRAFT INTERNATIONAL STANDARD ISO/FDIS 12810:2002(E)
Fluorocarbon refrigerants — Specifications and test methods
1 Scope
This International Standard defines the maximum levels of contaminants for various commercially available
fluorocarbon refrigerants and blends containing fluorocarbon refrigerants regardless of their source (new,
reclaimed or repackaged). This International Standard also establishes test methods for determining the levels
of these contaminants.
The fluorocarbon refrigerants included in this International Standard are those identified in ANSI/ASHRAE 34
as R 11, R 12, R 13, R 22, R 23, R 32, R 113, R 114, R 123, R 124, R 125, R 134a, R 143a, R 401A, R 401B,
R 402A, R 402B, R 500, R 502, and R 503.
NOTE Only those fluorocarbon refrigerants listed in ANSI/ASHRAE 34 are addressed in this International Standard.
2 Conformance
Refrigerants reported as conforming to this International Standard shall meet all of the requirements
established therein and shall be accompanied by a certificate of conformity indicating that the refrigerant does
not exceed the maximum contaminant levels specified in this International Standard.
3 Normative references
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.
ANSI/ASHRAE 34, Number designation and safety classification of refrigerants
4 Terms, definitions, symbols and abbreviated terms
4.1 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
4.1.1
contaminant
any substance foreign to the chemical and physical composition of the refrigerant (such as an impurity)
4.1.2
fluorocarbon
halogenated hydrocarbon containing fluorine
4.1.3
non-condensable
gas in a refrigerant that does not condense at the temperature and partial pressure at which it exists in the
condenser
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ISO/FDIS 12810:2002(E)
4.1.4
reclaimed refrigerant
refrigerant that has been processed to the requirements of this International Standard for reuse, by means
which may include distillation, at a reprocessing or manufacturing facility
NOTE Chemical analysis is required to determine that the appropriate product specifications have been met.
4.1.5
refrigerant
medium of heat transfer in a refrigerating system which absorbs heat on evaporating at a low temperature and
a low pressure and gives up heat on condensing at a higher temperature and higher pressure
4.1.6
repackaged refrigerant
refrigerant that has been relabelled or placed in another container for resale
4.2 Symbols and abbreviated terms
A Chromatographic peak area of component i
i
K Absolute response factor of the detector for component i
abs, i
K Relative response factor for component i
rel, i
m Mass of component i
i
p Vapour pressure of the refrigerant at the sampling temperature T
s s
s Standard deviation
t Temperature expressed in Celsius
T Sampling temperature expressed in kelvins (t + 273,15)
s
w Mass fraction of component i
i
a Temperature-to-pressure correlation factor for component i
i
j Volume fraction of component i
i
j Volume fraction determined at the sampling temperature T
s s
CL Confidence limit
ECN Effective carbon number
FID Flame ionization detector
FPT Female pipe thread
GC Gas chromatograph
ID Inner diameter
KF Karl Fischer
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ISO/FDIS 12810:2002(E)
MEK Methyl ethyl ketone
N/A Not applicable
NCG Non-condensable gas
NPT National pipe thread
OD Outer diameter
PTFE Polytetrafluoroethylene (Teflon)
RT Retention time
TCD Thermal conductivity detector
TCE Trichloroethylene
5 Characterization of refrigerants and requirements for contaminants
Refrigerant contaminants shall be characterized by measuring non-condensable components, water content,
and the presence of other impurities including other refrigerants, high boiling residues, particulates/solids,
acidity, and the presence of excessive chloride concentration. Requirements for the maximum contaminant
levels are specified in Tables 1 and 2. The tests or determining contaminants are specified in Clause 8.
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ISO/FDIS 12810:2002(E)
4 © ISO 2002 — All rights reserved
Table 1 — Characteristics of fluorocarbon refrigerants and maximum contaminant levels
Characteristics and Reporting Reference
R 11 R 12 R 13 R 22 R 23 R 32 R 113 R 114 R 123 R 124 R 125 R 134a R 143a
contaminants units subclause
a
CHARACTERISTICS
°C at
a
— 23,8 − 29,8 − 81,4 − 40,8 − 82,1 − 51,7 47,6 3,8 27,9 -12,1 − 48,1 − 26,2 − 47,0
Boiling point
d
101 325 Pa
a
°C — 0,3 0,3 0,5 0,3 0,5 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0,3
Boiling point range
0 µg/g 0 µg/g
0 % to 1 % 0 % to 30 % 0 % to 8 % 0 % to 5 %
Typical isomer content mass fraction — N/A N/A N/A N/A N/A N/A N/A to 5000 µg/g to 100 µg/g
R 113a R 114a R 123a R 124a
R 134 R 143
VAPOUR-PHASE
CONTAMINANTS
volume fraction,
Air and other non-
b b b
% 8.2.1 1,5 1,5 1,5 1,5 1,5 1,5 1,5 1,5 1,5 1,5
N/A N/A N/A
condensable
at 25 °C
LIQUID-PHASE
CONTAMINANTS
Water µg/g 8.2.2 20 10 10 10 10 10 20 10 20 10 10 10 10
All other impurities mass fraction,
8.2.3 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50
including refrigerants %
volume fraction,
High boiling residue 8.2.4 0,01 0,01 0,05 0,01 0,01 0,01 0,03 0,01 0,01 0,01 0,01 0,01 0,01
%
visually clean to
Particulates/solids 8.2.5 pass pass pass pass pass pass pass pass pass pass pass pass pass
pass
Acidity µg/g 8.2.6 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0
no visible
c
8.2.7 pass pass pass pass pass pass pass pass pass pass pass pass pass
Chlorides
turbidity
a
Boiling points and boiling point ranges, although not required, are provided for informational purposes.
b
Since R 11, R 113 and R 123 have normal boiling points at or above room temperature, non-condensable determinations are not required for these refrigerants.
c
Recognized chloride level for pass/fail is 3 µg/g.
d
101 325 Pa = 1 atm. The use of atmosphere is deprecated.
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ISO/FDIS 12810:2002(E)
© ISO 2002 — All rights reserved 5
Table 2 — Characteristics of fluorocarbon refrigerant mixtures and maximum contaminant levels
Reference
Characteristics and contaminants Reporting units R 401A R 401B R 402A R 402B R 500 R 502 R 503
subclause
a
CHARACTERISTICS
R 22/R 152a/ R 22/R 152a/ R 125/R 290/
Refrigerant components R 125/R 290/R 22 R 12/R 152a R 22/R 115 R 23/R 13
R 124 R 124 R 22
Nominal component mass fraction, % 53/13/34 61/11/28 60/2/38 38/2/60 73,8/26,2 48,8/51,2 40,1/59,9
51 to 55/ 59 to 63/ 58 to 62/ 36 to 40/
72,8 to 74,8/ 44,8 to 52,8/ 39 to 41/
Allowable component mass fraction, % 11,5 to 13,5/ 9,5 to 11,5/ 1 to 3/ 1 to 3/
25,2 to 27,2 47,2 to 55,2 59 to 61
33 to 35 27 to 29 36 to 40 58 to 62
°C
a
Boiling point − 33,0 to − 26,7 − 34,6 to − 28,6 − 48,9 to − 47,0 − 47,1 to − 44,9 − 33,5 − 45,4 − 88,7
c
at 101 325 Pa
a
°C — N/A N/A N/A N/A 0,5 0,5 0,5
Boiling point range
VAPOUR-PHASE CONTAMINANTS
Air and other non-condensable volume fraction, %
8.2.1 1,5 1,5 1,5 1,5 1,5 1,5 1,5
components at 25 °C
LIQUID-PHASE CONTAMINANTS
Water µg/g 8.2.2 10 10 10 10 10 10 10
All other impurities including
mass fraction, % 8.2.3 0,50 0,50 0,50 0,50 0,50 0,50 0,50
refrigerants
High boiling residue volume fraction, % 8.2.4 0,01 0,01 0,01 0,01 0,05 0,01 0,01
Particulates/solids visually clean to pass 8.2.5 pass pass pass pass pass pass pass
Acidity µg/g 8.2.6 1,0 1,0 1,0 1,0 1,0 1,0 1,0
b
no visible turbidity 8.2.7 pass pass pass pass pass pass pass
Chlorides
a
Boiling points and boiling point ranges, although not required, are provided for informational purposes.
b
Recognized chloride level for pass/fail is 3 µg/g.
c
101 325 Pa = 1 atm. The use of atmosphere is deprecated.
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ISO/FDIS 12810:2002(E)
6 Principle
The test methods for quantifying the various contaminants are specified in the following subclauses and shall
be the reference test methods. Alternate test methods specified in this International Standard are also
acceptable. If other test methods are employed, the user shall be able to demonstrate that they produce
results that are equivalent in terms of sensitivity, precision and accuracy as those specified in this International
Standard.
The recommended order for conducting these tests is to determine the quantity of the contaminants as
follows:
a) non-condensable components;
b) water content;
c) purity;
d) high-boiling residue;
e) particulates/solids;
f) acidity;
g) chloride.
7 Sampling
7.1 Precautions
Take special precautions to assure that representative samples are obtained for analysis. Sampling shall be
accomplished by trained personnel following accepted sampling and safety procedures.
7.2 Procedure
7.2.1 General
To assure accurate results, two separate refrigerant samples shall be obtained, i.e. one liquid-phase sample
and one vapour-phase sample, from the original packaged container, unless the final packaged cylinder is
provided.
7.2.2 Liquid-phase test samples
A liquid-phase sample is required for all tests listed in this International Standard except for the test for non-
condensable where a gaseous-phase test sample is required.
7.2.3 Vapour-phase test samples
A vapour-phase test sample shall be used for the determination of non-condensable. Non-condensable gases
consist primarily of air accumulated in the vapour phase of refrigerants. The solubility of air in the refrigerant
liquid phase is extremely low and air is not significant as a liquid-phase contaminant. The presence of non-
condensable gases may reflect poor quality control in transferring refrigerants to storage tanks and cylinders.
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ISO/FDIS 12810:2002(E)
8 Procedure
8.1 Product hazards
Avoid breathing refrigerant vapours. Volatile refrigerants shall be handled in a well-ventilated area to avoid
inhalation of refrigerant vapours. Compressed liquefied refrigerants can cause frostbite on contact. Liquefied
refrigerants will readily dissolve body oils. Consult the supplier's material safety data sheets (MSDS) for
additional safety information for each individual refrigerant as well as for each of the reagents associated with
the individual test methods.
8.2 Determination
8.2.1 Non-condensable contaminants
8.2.1.1 Test method
Determine the quantity of non-condensable contaminants using gas chromatography (GC) with a thermal
conductivity detector (TCD) as described in Annex A.
8.2.1.2 Requirements
The maximum level of non-condensable contaminants in the vapour phase of a refrigerant at 25 °C in a
container shall not exceed 1,5 % by volume, as indicated in Tables 1 and 2.
8.2.2 Water content
8.2.2.1 Reference test method
Determine the water content of refrigerants using coulometric Karl Fischer titration as the reference test
method as described in Annex B. Proper operation of the analytical method requires special equipment and
an experienced operator. Refrigerants containing a dye can be successfully analysed for water using this
method.
8.2.2.2 Alternative test method
The volumetric Karl Fischer titration is an acceptable alternative test method to the coulometric Karl Fischer
titration for determining the water content of refrigerants.
8.2.2.3 Requirements
The refrigerants covered in this International Standard shall have a maximum water content as indicated in
Tables 1 and 2.
8.2.3 Impurities including other refrigerants
8.2.3.1 Test method
Determine the amount of impurities, including other refrigerants, in the subject refrigerant using gas
chromatography as described in Annexes C to T.
NOTE A single gas chromatograph equipped with a thermal conductivity detector, a flame ionization detector and
packed and capillary columns can be used to conduct a number of test methods.
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ISO/FDIS 12810:2002(E)
8.2.3.2 Requirements
The subject refrigerant shall not contain more than 0,50 % by mass of impurities excluding non-condensable
but including other refrigerants as indicated in Tables 1 and 2.
8.2.4 High boiling residue
8.2.4.1 Test method
Determine the high boiling residue by measuring the residue after evaporation of a standard volume of
refrigerant at a temperature 28 °C above the boiling point of the test sample, using a Goetz tube as specified
in Annex U. Oils and organic acids are determined by this method.
8.2.4.2 Alternative test method
An alternative gravimetric test method is also described in Annex U.
8.2.4.3 Requirements
The value for high boiling residue shall be expressed as a percentage by volume and shall not exceed the
maximum percent specified in Tables 1 and 2.
8.2.5 Particulates/solids
8.2.5.1 Test method
Determine the presence of particulates/solids using the test method described in U.7.3.1 or U.7.3.2 of
Annex U.
Evaporate a measured amount of the liquid test sample from a Goetz bulb under controlled temperature
conditions. Determine the particulates/solids by visual examination of the Goetz bulb after evaporation of the
refrigerant.
8.2.5.2 Requirements
The presence of any dirt, rust or other particulate contamination shall be reported as “fail.”
8.2.6 Acidity
8.2.6.1 Test method
The acidity test uses the titration principle to detect any compound that is soluble in water and ionizes as an
acid.
Determine the acidity of the test sample using the test method described in Annex V. This test is not suitable
for determination of high molecular mass organic acids.
8.2.6.2 Requirements
1)
The maximum permissible acidity is 1 µg/g expressed as hydrochloric acid as indicated in Tables 1 and 2.
1) 1 µg/g = 1 ppm. The use of parts per million is deprecated.
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ISO/FDIS 12810:2002(E)
8.2.7 Chloride
8.2.7.1 Test method
Test the refrigerant for chloride as an indication of the presence of hydrochloric acid and/or metal chlorides.
Significant amounts of oil in refrigerants may interfere with the results by indicating a failure in the absence of
chloride.
Determine the presence of chloride using the test method described in Annex W.
NOTE The test will show noticeable turbidity at chloride levels of about 3 µg/g or higher.
8.2.7.2 Requirements
The results of the test shall not exhibit any sign of turbidity. Report the results as “pass” or “fail”. If a
quantitative test method is used, the maximum chloride content shall be 3 µg/g.
9 Test report
The test report shall include the following information:
a) all information necessary for the identification of the sample tested, notably the source of the packaged
refrigerant (manufacturer, re-claimer or re-packager);
b) a reference to this International Standard, i.e. ISO 12810;
c) the identity of the refrigerant, i.e. the accepted refrigerant number as specified in ANSI/ASHRAE 34;
d) the method used for determining the contamination level;
e) the results of the tests, including the contaminant levels which shall be reported as follows:
1) air and other non-condensable: % by volume at 25 °C
2) water: µg/g
3) chlorides: pass/fail
4) acidity: µg/g as hydrochloric acid
5) high boiling residue: % by volume
6) particulates/solids: pass/fail
7) all other impurities including refrigerants
...
ISO/FDIS 12810:2002(E)
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ISO/FDIS 12810:2002(E)
Annex I
(normative)
Determination of purity of new and reclaimed refrigerant 113
by gas chromatography
I.1 Applicability
This test method is used for the determination of the impurities typically present in new and reclaimed 1,2,2-
trichlorotrifluoroethane (R 113) by gas chromatography.
Detection limits are given in Table I.1 for this method.
I.2 Principle
The organic purity of new and reclaimed R 113 is determined by programmed temperature gas
chromatography using a capillary column and flame ionization detector (FID). Component peak areas are
integrated electronically and quantified by the area-normalization response-factor method.
Table I.1 — Detection limits and precision results for common impurities in R 113
Component Detection Range investigated Repeatability limit at Relative mean
limit 95 % confidence limit error
µg µg µg %
R 115 5 50 1,2 1,3
R 1113 2 60 2,3 − 0,7
R 12 10 70 0,8
− 1,2
R 22 5 70 0,8 1,0
R 114 5 40 0,7 0,8
R 216ba 2 50 2,5 − 1,9
R 133a 1 50 0,7
− 2,3
R 1112a 2 20 0,3 − 3,3
R 11 15 120 4,1 0,8
R 316bb 2 30 6,8 − 1,1
R 123a 2 50 1,3
− 2,5
R 123 2 50 1,5
− 1,1
R 225da 1 30 0,9
− 2,1
R 318mbb 2 30 0,8
− 0,7
R 122 2 80 2,3
0,4
R 10 5 100 4,7 2,6
R 112 3 75 2,5
− 1,1
R 1120 2 30 1,4 0,3
R 1110 2 30 1,7
0,8
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ISO/FDIS 12810:2002(E)
I.3 Limitations and interferences
The calibration required by this method is only applicable to those impurities commonly present (listed in
Table I.1) in R 113. Using this column, due to the effect of R 113, the R 316bb peak is distorted and appears
as a triplet centered at 16 min. Nonetheless, the integration of this peak is reproducible. Although the identity
of the HCFC225 isomer(s) is uncertain, the HCFC225da isomer is used for calibration because it is
commercially available. Any impurities eluting under the comparatively large R 113 peak cannot be detected
using this method.
I.4 Reagents
I.4.1 R 113 reference standard of the highest purity R 113 available and impurity reference standards,
for calibration standard preparation.
Predetermine the purity of each calibration component using a gas chromatograph equipped with a flame
ionization detector (FID) and/or a thermal conductivity detector (TCD) and, if necessary, equipped with a mass
spectrometer (GC-MS).
I.5 Apparatus
Equivalents may be substituted for the following apparatus.
32)
I.5.1 GC [HP 5890 ], equipped with an FID.
33)
I.5.2 Capillary column: Rtx-1301 , 105 m × 0,25 mm ID, 1,0 µm film thickness.
34)
I.5.3 Data acquisition system [HP 3396 integrator ], for the GC.
I.5.4 Serum bottle, 125 ml nominal capacity.
NOTE The brimful capacity is 160 ml.
I.5.5 Septa, 20 mm.
I.5.6 Glass sampling bulb, 125 ml capacity.
Enlarge the side outlet opening to accommodate a crimp-on 20 mm septum. Apply fiberglass tape outside for
protection.
I.5.7 Syringe, for liquid sample volumes of 2 µl.
I.5.8 Deflected point needles, size No. 22.
32) Hewlett Packard Model 5890 is an example of a suitable GC available commercially. This information is given for the
convenience of users of this International Standard and does not constitute an endorsement by ISO of this product.
Equivalent products may be used if they can be shown to lead to the same results.
33) Rtx-1301 is the trade name of a product supplied by Resteck Corp., 110 Benner Circle, Bellefonte, PA. This
information is given for the convenience of users of this International Standard and does not constitute an endorsement by
ISO of the product named. Equivalent products may be used if they can be shown to lead to the same results.
34) Hewlett Packard Model 3396 is an example of a suitable integrator available commercially. This information is given
for the convenience of users of this International Standard and does not constitute an endorsement by ISO of this product.
Equivalent products may be used if they can be shown to lead to the same results.
© ISO 2002 — All rights reserved 87
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ISO/FDIS 12810:2002(E)
I.6 Sampling
Submitted test samples should be in either metal cylinders or in glass or plastic bottles such that the
containers are between 60 % and 80 % full of liquid.
I.7 Procedure
I.7.1 Safety considerations
Work under a laboratory hood whenever possible. Wear gloves and a face shield when working with the
unsaturated impurities used for the calibration standards.
Take special precautions when handling medium- and high-pressure refrigerants in this procedure. Contact
with skin may cause frostbite. Avoid inhalation of refrigerant vapours. Keep all cylinder valves capped when
not in use. Make certain sample cylinders are not overfilled.
Review all relevant Material Safety Data Sheets (MSDS) before performing this analysis.
I.7.2 Chromatograph operating conditions
Use the following chromatograph conditions.
Detector FID
Detector temperature 250 °C
Carrier gas flow rate approximately 1 ml/min He
Auxiliary flow 30 ml/min He
Split ratio 30:1
Injection port temperature 200 °C
Column head pressure 200 kPa
Column Rtx-1301 capillary column
Initial column temperature 35 °C
Initial hold time 10 min
Oven temperature program 8 °C/min
Final column temperature 160 °C
Post hold time 8 min
Test-sample volume injected 2 µl
Column maximum
allowable temperature
(for conditioning purposes) 280 °C
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ISO/FDIS 12810:2002(E)
I.7.3 Calibration
I.7.3.1 Preparation of primary calibration standard
I.7.3.1.1 Determine the tare mass of a clean, dry 125 ml serum bottle (I.5.4) to the nearest 0,000 1 g.
I.7.3.1.2 Add a small crystal of R 112 (0,02 g) and reweigh. Record the exact value of the mass,
expressed in micrograms, of R 112 in Table I.2 in the fourth column.
I.7.3.1.3 Confirm that the R 113 reference standard (I.4.1) is of the highest purity after inspection of the
chromatogram obtained under the operating conditions given in I.7.2.
The purest R 113 reference standard will contain some of the impurities listed in Table I.1. Determine the
amounts of impurities present in the R 113 reference standard using the method of standard additions, i.e. by
spiking the R 113 reference standard with component impurities at microgram per gram levels. The increase
in the peak areas of the corresponding impurity is directly proportional to the amount of impurity added. The
quantity of impurity present initially in the R 113 reference standard can be extrapolated and the total quantity
of component impurity determined in the calibration standard.
I.7.3.1.4 Weigh the 125 ml serum bottle (I.7.3.1.2) with cap and septum (I.5.5) loosely attached and
determine the second tare mass (to the nearest 0,01 g). Then fill this bottle with the R 113 reference standard
to within 16 mm of the top. Crimp-on the septum.
I.7.3.1.5 Reweigh and subtract the second tare mass in I.7.3.1.4 to obtain the mass, expressed in grams,
of R 113 added.
I.7.3.1.6 Add the volume of each calibration component specified in Table I.2, individually, and in turn,
through the septum and below the R 113 liquid surface in the bottle. Use an appropriately sized millilitre gas-
tight syringe with deflected point needles for gases and a liquid microlitre syringe for liquids. Shake the bottle
to mix after addition of each component.
To preserve the stock of calibration gases, it is suggested to load a small evacuated 125 ml gas sampling bulb
to 101 325 Pa from the liquid phase as illustrated in Figure I.1. The appropriate volume is then withdrawn and
injected into the serum bottle containing the R 113. For impurities which are liquids at ambient temperature,
inject the indicated volume (see Table I.2) of each respective component into the serum bottle.
I.7.3.1.7 Sum the masses in the “Mass of component added” column of Table I.2. Add this sum to that
determined in I.7.3.1.5 to obtain the total mass of the calibration standard (to the nearest 0,01 g) in the bottle.
I.7.3.1.8 Calculate the mass fraction (to the nearest µg/g) for each component added in the calibration
standard by dividing the mass of each component added by the total mass of sample in the serum bottle (see
I.7.3.1. 7).
I.7.3.1.9 Calculate the total mass fraction of each component present in the calibration standard by
combining the mass fraction present in the R 113 reference standard (if any) (see I.7.3.1.3) to the mass
fraction of the component added. The values of the total mass fraction of each component present in the
calibration standard are those used for determining the method response factors.
I.7.3.1.10 Place the serum bottle calibration standard in an ice bath and, after it is ice cold, remove and
immediately replace with a new septum.
I.7.3.1.11 Record the total mass of the calibration standard (I.7.3.1.7), the serum bottle tare mass (second
tare mass determined in I.7.3.1.4 less the mass of R 112 added determined in I.7.3.1.2) and the date of
preparation on the bottle label. Store in a refrigerator. Use this calibration standard until the mass contained in
Cylinder 1 drops to 60 %, i.e. 60 % of the mass measured in I.7.3.1.7. Once it drops below 60 %, discard this
calibration standard and prepare a new one so as to avoid the possibility of the vapour-liquid equilibrium
changing slightly, thereby changing the composition of the liquid phase.
© ISO 2002 — All rights reserved 89
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ISO/FDIS 12810:2002(E)
Key
1 calibration chemical cylinder 4 septum (2 cm) 7 valve C 10 vacuum
2 liquid phase 5 valve B 8 vacuum gauge
3 valve A 6 gas sampling bulb 9 valve D
Figure I.1 — Apparatus used for calibration standard preparation
I.7.3.2 Determination of component response factors
I.7.3.2.1 Set up the integrator for an area-normalization response-factor calibration.
NOTE Depending upon the integrator used, it is often more desirable to convert the µg/g (part per million) values to
mass fraction expressed as a percentage for response factor calculations and for reporting purposes.
I.7.3.2.2 Analyse the calibration standard in triplicate using the chromatographic conditions given in I.7.2.
I.7.3.2.3 Using R 113 as the reference peak, program the integrator to determine the relative response
factor (K ) for each component which is then stored. Calculate the absolute response factor K for each
rel,i abs,i
component i as follows:
w
i,cal
K = (I.1)
abs,i
A
i
where
K is the absolute response factor for component i;
abs,i
w is the mass fraction of component i in the calibration standard;
i,cal
A is the peak area of component i (average of three determinations).
i
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ISO/FDIS 12810:2002(E)
Table I.2 — Primary calibration standard components
Component Relative molecular Volume Mass of Mass fraction Total mass
mass added component of fraction of
a
component component
added
b c
added present
µg µg/g µg/g
ml
d
R 115
154 2,0 12 653 53
d
R 1113 116 3,0 14 294 60
d
R 12
121 3,5 17 336 72
d
R 22 86 5,0 17 690 74
d
R 114
171 1,5 10 502 44
R 216ba 221 8 µl 12 722 53
d
R 133a
118 2,5 12 137 50
d
R 1112a 133 0,8 4 349 18
R 11
137 20 µl 29 000 121
R 123a 153 8 µl 11 984 50
R 123
153 8 µl 11 984 50
R 225da 203 5 µl 7 782 32
R 318mbb
271 5 µl 8 400 35
R 122 169 5 µl 7 723 32
R C-316bb 233 5 µl 7 650 32
R 112 204 — 20 000 83
TCE 131 5 µl 7 278 30
PCE 166 5 µl 8 156 34
R 10 154 15 µl 23 925 100
a
If necessary, correct the value of the mass added for the purity of the calibration component previously
established.
b
Values shown are given for illustration; exact values are determined in I.7.3.1.8.
c
Column to be filled in I.7.3.1.9 after determining total mass fraction present in reference standard R 113
(see I.7.3.1.3).
d
These impurities are gases at ambient room temperature, the others are liquids with low boiling points. For
R 1112a, warm the vial or cylinder and sample the headspace vapour.
And for R 113
100,000- w
tot,imp
K = (I.2)
abs,113
A
113
where
K is the absolute response factor for component i;
abs,113
w is the mass fraction, expressed as a percentage, of the sum of all impurities;
tot,imp
A is the peak area of R 113 (average of three determinations).
113
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ISO/FDIS 12810:2002(E)
Then, using R 113 as the reference peak:
KK
abs,i abs,113
KK=== 1, 0
rel,i rel,113
KK
abs,113 abs,113
where K is the value of the relative response factor for component i, computed to the nearest 0,000 1 unit.
rel,i
I.7.4 Determination
Analyse the sample using the chromatographic conditions given in I.7.2. Because of the relatively high boiling
temperature of R 113 (47 °C), it is not necessary to pre-cool the microlitre sampling syringe. Use component
spiking and/or GC-MS (if available) to identify questionable peaks.
A typical chromatogram of R 113 is given in Figure I.2.
I.8 Calculation
The mass fraction, expressed as a percentage, of each component is calculated as follows:
KA××100
rel,ii
w = (I.3)
i
AK×
()
Âiirel,
where
w is the mass fraction, expressed as a percentage, of component i in the test sample;
i
K is the relative response factor for component i;
rel, i
A is the peak area of component i;
i
AK× is the sum of all component peak areas times their respective relative response factors.
( )
Âiirel,
I.9 Precision
Statistical parameters for each impurity are listed in Table I.1. The data were obtained by analysing an R 113
calibration mixture seven times within a one-day period by one operator.
I.10 Test report
Report sample component mass fractions to the nearest 0,000 1 % (or to the nearest µg/g). If results are less
than the individual detection limits (see Table I.1), then report “< the detection limit (DL) value given”.
92 © ISO 2002 — All rights reserved
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ISO/FDIS 12810:2002(E)
RT Com-
ponent
min
9,60 R 115
10,24 R 1113
10,41 R 12
10,54 R 22
11,10 R 114
12,41 R 216ba
12,65 R 133a
13,72 R 1112a
14,51 R 318mmb
15,06 R 11
16,00 R C-316bb
16,35 R 123a
16,59 R 123
17,30 R 113
18,51 R 225
23,26 R 10
23,49 R 122
24,68 R 112a
24,81 R 112
25,06 R 1120
28,76 R 1110
Figure I.2 — Gas chromatogram of R 113
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ISO/FDIS 12810:2002(E)
Annex J
(normative)
Determination of purity of new and reclaimed refrigerant 114
by gas chromatography
J.1 Applicability
This test method is used for the determination of the impurities typically present in new and reclaimed
1,2-dichlorotetrafluoroethane (R 114) by gas chromatography.
Detection limits are given in Table J.1 for this method.
J.2 Principle
The organic purity of new and reclaimed R 114 is determined by programmed temperature gas
chromatography using a packed column and flame ionization detector (FID). Component peak areas are
integrated electronically and quantified by the area-normalization response-factor method.
Table J.1 — Detection limits and precision results for common impurities in R 114
Component Detection limit Range investigated Repeatability limit at Relative mean
95 % confidence limit error
µg µg µg %
R 23 2 15 0,28 − 3,2
R 13 3 25 0,44 − 3,8
R 152a 1 25 0,40 0,8
R 22 2 60 0,67 1,7
R 115 2 100 1,67 1,1
R 12 2 60 0,91 − 1,1
R 124a 1 15 0,75 − 2,3
R 124 1 30 0,50 1,6
R 133a 1 50 0,50 1,1
R 217ca 2 20 0,67 2,7
R 217ba 2 20 1,33 − 3,4
R 11 4 45 0,67 1,7
R 123a 2 25 0,50 − 2,7
R 123 2 65 0,77 − 3,4
R 113 2 50 1,1 − 3,7
R 113a 2 30 1,23 − 2,7
R 122 2 30 0,67 − 1,3
TCE 2 30 0,33 − 2,3
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ISO/FDIS 12810:2002(E)
J.3 Limitations and interferences
The calibration required by this method is only applicable to those impurities commonly present (listed in
Table J.1) in new and reclaimed R 114. Any impurities eluting under the comparatively large R 114 peak
cannot be detected using this method. Furthermore, R 30, if present, will coelute with CFC217ca and R 21 will
coelute with CFC217ba. R 30 and R 21 are not normally present in R 114.
J.4 Reagents
J.4.1 R 114 reference standard, of highest purity R 11 available and impurity reference standards, for
calibration standard preparation.
Predetermine the purity of each calibration component using a gas chromatograph equipped with a flame
ionization detector (FID) and/or a thermal conductivity detector (TCD) and, if necessary, equipped with a mass
spectrometer (GC-MS).
J.5 Apparatus
Equivalents may be substituted for the following apparatus.
35)
J.5.1 GC [HP 5890 ], equipped with an FID.
36)
J.5.2 Packed column: 1 % SP-1 000 on Carbopack B , 24 feet × 1/8 inch OD, stainless steel, 60 mesh
to 80 mesh.
37)
J.5.3 Data acquisition system [HP 3396 integrator ], for the GC.
J.5.4 Septa, 20 mm.
J.5.5 Glass sampling bulbs, 125, 250 and 500 ml capacities.
Enlarge the side outlet opening to accommodate a crimp-on 20 mm septum. Apply fiberglass tape outside for
protection.
J.5.6 Syringe, for gas sample volumes of 0,50 ml.
J.5.7 Deflected point needles, size No. 22.
J.5.8 Swivel union, 1/4 inch SAE.
35) Hewlett Packard Model 5890 is an example of a suitable GC available commercially. This information is given for the
convenience of users of this International Standard and does not constitute an endorsement by ISO of this product.
Equivalent products may be used if they can be shown to lead to the same results.
36) 1 % SP-1 000 on Carbopack B is the trade name of a product supplied by Supelco, Bellefonte, PA. This information is
given for the convenience of users of this International Standard and does not constitute an endorsement by ISO of the
product named. Equivalent products may be used if they can be shown to lead to the same results.
37) Hewlett Packard Model 3396 is an example of a suitable integrator available commercially. This information is given
for the convenience of users of this International Standard and does not constitute an endorsement by ISO of this product.
Equivalent products may be used if they can be shown to lead to the same results.
© ISO 2002 — All rights reserved 95
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ISO/FDIS 12810:2002(E)
J.6 Sampling
Submitted sample cylinders shall contain sufficient liquid phase, preferably between 60 % and 80 % full of
liquid, for analysis.
J.7 Procedure
J.7.1 Safety considerations
Work under a laboratory hood whenever possible. Wear gloves and a face shield when working with the
unsaturated impurities used for the calibration standards.
Take special precautions when handling medium- and high-pressure refrigerants in this procedure. Contact
with skin may cause frostbite. Avoid inhalation of refrigerant vapours. Keep all cylinder valves capped when
not in use. Make certain sample cylinders are not overfilled.
Review all relevant Material Safety Data Sheets (MSDS) before performing this analysis.
J.7.2 Chromatograph operating conditions
Use the following chromatograph conditions.
Detector FID
Detector temperature 250 °C
Carrier gas flow rate 30 ml/min He
Injection port temperature 200 °C
Test-sample volume injected 0,50 ml
Column 1 % SP-1 000 on Carbopack B packed column
Initial column temperature 40 °C
Initial hold time 6 min
Oven temperature program 10 °C/min
Final column temperature 175 °C
Post hold time 18 min
Column maximum
allowable temperature
(for conditioning purposes) 225 °C
J.7.3 Calibration
J.7.3.1 Preparation of primary calibration standard
J.7.3.1.1 Crimp-on the septum (J.5.4), then determine the internal volume of the 500 ml gas sampling bulb
(J.5.5) by weighing the bulb empty, then filled to maximum capacity with water and determine the difference in
mass, expressed in grams, of water. Estimating the density of water to be 1,0 g/ml, convert this difference in
96 © ISO 2002 — All rights reserved
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ISO/FDIS 12810:2002(E)
mass to volume, expressed in millilitres. Record this difference in volume as the internal capacity of the bulb
(to the nearest 1,0 ml).
J.7.3.1.2 Assemble the apparatus as illustrated in Figure J.1.
Key
1 calibration chemical cylinder 4 septum (2 cm) 7 valve C 10 vacuum
2 liquid phase 5 valve B 8 vacuum gauge
3 valve A 6 gas sampling bulb 9 valve D
Figure J.1 — Vacuum-sampling apparatus
J.7.3.1.3 Attach a cylinder of high purity R 114 (J.4.1) to the 500 ml gas sampling bulb (J.5.5).
The purest R 114 reference standard will contain some of the impurities listed in Table J.1. Determine the
amounts of impurities present in the R 114 reference standard using the method of standard additions, i.e. by
spiking the R 114 reference standard with component impurities at microgram per gram levels. The increase
in the peak areas of the corresponding impurity is directly proportional to the amount of impurity added. The
quantity of impurity present initially in the R 114 reference standard can be extrapolated and the total quantity
of component impurity determined in the calibration standard.
J.7.3.1.4 With valve “A” closed (see Figure J.1), open all other valves and evacuate the gas sampling bulb
to a pressure of 133,3 Pa (1 mm of Hg).
J.7.3.1.5 Close valve “D” (see Figure J.1) and monitor the gauge for several minutes to ensure that the
system does not leak.
J.7.3.1.6 Slowly open valve “A” (see Figure J.1) and flash-vaporize liquid-phase R 114, increasing the
system pressure to 101 325 Pa. Close valve “A.”
J.7.3.1.7 Repeat steps J.7.3.1.4 to J.7.3.1.6.
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ISO/FDIS 12810:2002(E)
J.7.3.1.8 Close valves “B” and “C” (see Figure J.1) and remove the bulb from the vacuum-sampling
apparatus.
J.7.3.1.9 Calculate the mass, expressed in grams, of R 114 added, m , to the bulb as follows:
114
170,4 ×V
b
m = (J.1)
114
24 450
where
170,4 is the relative molecular mass of R 114;
V is the internal volume, expressed in millilitres, of the bulb (determined in J.7.3.1.1);
b
24 450 is the volume, expressed in millilitres, occupied by 1 mol of R 114 at 25 °C and at 101 325 Pa.
J.7.3.1.10 Add the volume of each calibration component specified in the Table J.2, individually, and in turn,
to the sampling bulb. Use an appropriately sized microlitre or millilitre gas-tight syringe with deflected point
needles.
To preserve the stock of calibration components, it is suggested to load a small evacuated 125 ml gas
sampling bulb to 101 325 Pa from the liquid phase as illustrated in Figure J.1. The appropriate volume is then
withdrawn and injected into the 500 ml sampling bulb.
J.7.3.1.11 Into a 30 ml nominal capacity (37 ml brimful) serum bottle, capped and crimped with a septum,
add the exact volumes of the liquid impurities specified in Table J.3 in the order given so as to prepare the
standard solution.
Using a syringe, inject each component through the septum of the serum bottle. Use a No. 22 needle (or
smaller) as a vent. After addition, shake the bottle vigorously to mix it. Label, date and store the standard
solution in a refrigerator.
J.7.3.1.12 Refer to Figure J.1. First evacuate a 250 ml bulb (the internal volume is to have been measured
according to J.7.3.1.1), then fill it to a pressure of 101 325 Pa with R 114 reference standard.
J.7.3.1.13 Accurately withdraw and inject exactly 20,0 µl of standard solution (J.7.3.1.11) into the 250 ml
bulb. Allow the mixture to equilibrate for 30 min.
J.7.3.1.14 Using a 10 ml gas-tight syringe, withdraw vapour from the 250 ml bulb and inject exactly 10,0 ml
into the 500 ml sampling bulb. The mass, expressed in micrograms, of each component thus added is
calculated according to equation (J.2) and is recorded in column four of Table J.2:
m × 200 000
liq,i
m = (J.2)
cal,i
32 ×V
b
where
m is the mass of component i, expressed in micrograms, added to the primary calibration
cal,i
standard;
m is the mass, expressed in grams, of the liquid component i added to the standard solution as
liq,i
specified in Table J.3 (see J.7.3.1.11);
V is the internal volume, expressed in millilitres, of the 250 ml sampling bulb (see J.7.3.1.12);
b
32 is the total approximate volume, expressed in millilitres, of solution prepared in J.7.3.1.11;
98 © ISO 2002 — All rights reserved
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ISO/FDIS 12810:2002(E)
200 000 is the dilution and conversion (grams to micrograms) factor.
J.7.3.1.15 Sum the masses in the “Mass of component added” column of Table J.2 and combine this mass
with that of J.7.3.1.9 to obtain the total mass of sample (to the nearest 0,000 1 g) in bulb.
J.7.3.1.16 Calculate the mass fraction (to the nearest µg/g) for each component added in the calibration
standard by dividing the mass of each component added by the total mass of sample in the gas bulb (see
J.7.3.1.15).
Table J.2 — Primary calibration standard components
Component Relative Volume Mass of Mass Total mass
molecular mass added component fraction of fraction of
a
component component
added
b c
added present
µl µg µg/g µg/g
R 23 70 20 57,2 15
R 13 104 20 85,6 22
R 152a 66 35 94,5 26
R 22 86 65 230,0 60
R 115 154 60 379,2 98
R 12 121 50 247,2 64
R 124a 136 10 55,8 14
R 124 136 20 111,7 29
R 133a 118 40 193,8 50
R 217ca 204 10 83,6 22
e
R 217ba 204 10 83,6 22
d f
R 11 137 — 75
d f
R 123a 153 — 19
d f
R 123 153 — 37
d f
R 113a 188 — 40
d f
R 113 188 — 60
d f
R 122 169 — 39
d f
TCE 131 — 37
a
If necessary, correct the mass of component added for the purity of the calibration component previously
established.
b
Values shown are given for illustration; exact values are determined in J.7.3.1.15.
c
Column to be filled in J.7.3.1.17 after determining total mass fraction present in reference standard R 114
reference standard (see J.7.3.1.3).
d
These components are liquids at ambient laboratory temperature and are added to the 500 ml bulb as
described in J.7.3.1.11 to J.7.3.1.14.
e
Note that CFC 217ba often contains 15 % to 20 % of the CFC 217ca isomer.
f
From J.7.3.1.14.
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ISO/FDIS 12810:2002(E)
Table J.3 — Preparation of the standard solution containing liquid components
for the primary calibration standard
Component Volume added Density at 20 °C Mass
ml g/ml g
TCE 4,0 1,456 5,824
R 122 4,0 1,544 6,176
R 113 6,0 1,565 9,390
R 113a 4,0 1,579 6,316
R 123a 2,0 1,492 2,984
R 123 4,0 1,470 5,880
R 11 8,0 1,487 11,896
J.7.3.1.17 Calculate the total mass fraction of each component present in the calibration standard by
combining the mass fraction present in the R 114 reference standard (if any) to the mass fraction of the
component added (see J.7.3.1.3). The values of the total mass fraction of each component present in the
calibration standard are those used for determining the method response factors.
J.7.3.1.18 Allow the gas sampling bulb to stand for 20 min to 30 min to equilibrate. The primary calibration
standard will be stable for 3 days to 4 days.
J.7.3.2 Determination of component response factors
J.7.3.2.1 Set up the integrator for an area-normalization response-factor calibration.
NOTE Depending upon the integrator used, it is often more desirable to convert the µg/g (part per million) values to
mass fraction expressed as a percentage for response factor calculations and for reporting purposes.
J.7.3.2.2 Analyse the contents of the calibration standard bulb in triplicate using the chromatographic
conditions given in J.7.2.
J.7.3.2.3 Using R 114 as the reference peak, program the integrator to determine the relative response
factor (K ) for each component which is then stored. Calculate the absolute response factor K for each
rel,i abs,i
component i as follows:
w
i,cal
K = (J.3)
abs,i
A
i
where
K is the absolute response factor for component i;
abs,i
w is the mass fraction of component i in the calibration standard;
i,cal
A is the peak area of component i (average of three determinations).
i
And for R 114
100,000- w
tot,imp
K = (J.4)
abs,11
...
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