BRITISH STANDARD BS EN ISO

6326-3:1998
BS
3156-11.4.3:
1994
Incorporating

Natural gas
Amendment No. 1 to
BS 3156-11.4.3:1994
(renumbers the BS as

Determination of sulfur
BS EN ISO 6326-3:
1998)

compounds
Part 3: Determination of hydrogen
sulfide, mercaptan sulfur, and carbonyl
sulfide sulfur by potentiometry

ICS 75.060
BS EN ISO 6326-3:1998

Committees responsible for this

British Standard

The preparation of this British Standard was entrusted to Technical

Committee PTI/15, Natural gas and gas analysis upon which the following
bodies were represented:

AEA Technology
British Coal Corporation
British Compressed Gases Association
British Gas plc
British Glass Manufacturers Confederation
Chemical Industries Association
Department of Trade and Industry (Gas and Oil Measurement Branch)
Department of Trade and Industry (National Physical Laboratory)
Institute of Petroleum
Institution of Gas Engineers
Sira Limited
Society of Chemical Industry
Society of Glass Technology

This British Standard, having

been prepared under the
direction of the Materials and
Chemicals Sector Board (I/-),
was published under the
authority of the Standards
Board and comes
into effect on
15 December 1994 Amendments issued since publication
BSI 04-1999
Amd. No. Date Comments

The following BSI references 9993 June 1998 Indicated by a sideline in the margin
relate to the work on this
standard:
Committee reference PTI/15
Special announcement in
BSI News, September 1994

ISBN 0 580 23614 5

 BS EN ISO 6326-3:1998

Contents

Page
Committees responsible Inside front cover
National foreword ii
Foreword 2
1 Scope 3
2 Normative references 3
3 Principle 3
4 Reagents and materials 3
5 Apparatus 3
6 Sampling 4
7 Procedure 4
8 Expression of results 5
9 Test report 6
Figure 1 Test apparatus 5
Figure 2 Example of a titration curve 6
Table 1 Precision data 7
List of references Inside back cover

BSI 04-1999 i
BS EN ISO 6326-3:1998

National foreword

This British Standard has been prepared by Technical Committee PTI/15, and is
the English language version of EN ISO 6326-3:1997 Natural gas
Determination of sulfur compounds Part 3: Determination of hydrogen
sulfide, mercaptan sulfur and carbonyl sulfide sulfur by potentiometry, published
by the European Committee for Standardization (CEN). It is identical with
ISO 6326-3:1989, published by the International Organization for
Standardization (ISO). ISO 6326-3 was prepared by Technical Committee 158,
Analysis of gases, in which the United Kingdom participated.
BS EN ISO 6326-3 retains the secondary identifier BS 3156-11.4.3, so that it
remains cross-referenced within the BS 3156 series of standards. Each
Subsection of Section 11.4 of BS 3156 is identical with the corresponding Part of
ISO 6326, and Section 11.4 of BS 3156 consists of the following Subsections:
Subsection 11.4.1 Introduction
Subsection 11.4.2 Odoriferous sulfur compounds by gas chromatography
using an electrochemical detector
Subsection 11.4.3 Hydrogen sulfide, mercaptan sulfur, and carbonyl
(BS EN ISO 6326-3) sulfide sulfur by potentiometry
Subsection 11.4.4 Hydrogen sulfide, carbonyl sulfide and
sulfur-containing odorants by gas chromatography
using a flame photometric detector
Subsection 11.4.5 Lingener combustion method
(BS EN ISO 6326-5)

In the United Kingdom the preferred method is that given in Subsection 11.4.4 of
BS 3156. The flame photometric detector is available from most manufacturers of
chromatographs, both laboratory and process units, and is applicable to any
sulfur compound. By contrast, the electrochemical detector is available from a
single supplier and is operated under completely different conditions in order to
measure carbonyl sulfide, to those used for all other sulfur compounds.
Cross-reference
Publication referred to Corresponding British Standard
ISO 1042:1983 BS 1792:1982 Specification for one-mark volumetric flasks
A British Standard does not purport to include all the necessary provisions of a
contract. Users of British Standards are responsible for their correct application.
Compliance with a British Standard does not of itself confer immunity
from legal obligations.

Summary of pages
This document comprises a front cover, an inside front cover, pages i and ii,
the EN title page, pages 2 to 8, an inside back cover and a back cover.
This standard has been updated (see copyright date) and may have had
amendments incorporated. This will be indicated in the amendment table on
the inside front cover.

ii BSI 04-1999
EUROPEAN STANDARD EN ISO 6326-3
NORME EUROPENNE
December 1997
EUROPISCHE NORM

ICS 75.060

Descriptors: Natural gas, gas analysis, determination of content, sulfur, potentiometric methods

English version

Natural gas Determination of sulfur compounds

Part 3: Determination of hydrogen sulfide, mercaptan
sulfur and carbonyl sulfide sulfur by potentiometry
(ISO 6326-3:1989)

Gaz naturel Dtermination des composs Erdgas Bestimmung von

soufrs Partie 3: Dtermination du sulfure Schwefelverbindungen Teil 3: Bestimmung
dhydrogne, des thiols et du sulfure de von Schwefelwasserstoff, Mercaptanschwefel
carbonyle par potentiomtrie und Kohlenstoffoxidsulfidschwefel durch
(ISO 6326-3:1989) Potentiometrie
(ISO 6326-3:1989)

This European Standard was approved by CEN on 6 November 1997.

CEN 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 Central Secretariat or to any CEN 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 CEN member into its own language and notified to the
Central Secretariat has the same status as the official versions.
CEN members are the national standards bodies of Austria, Belgium,
Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland,
Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden,
Switzerland and United Kingdom.

CEN
European Committee for Standardization
Comit Europen de Normalisation
Europisches Komitee fr Normung
Central Secretariat: rue de Stassart 36, B-1050 Brussels

1997 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national
Members
Ref. No. EN ISO 6326-5:1997 E
EN ISO 6326-3:1997

Foreword
The text of the International Standard from
Technical Committee ISO/TC 193, Natural gas, of
the International Organization for Standardization
(ISO) has been taken over as a European Standard
by CEN/CS.
This European Standard shall be given the status of
a national standard, either by publication of an
identical text or by endorsement, at the latest by
June 1998, and conflicting national standards shall
be withdrawn at the latest by June 1998.
According to CEN/CENELEC Internal Regulations,
the national standards organizations of the
following countries are bound to implement this
European Standard: Austria, Belgium,
Czech Republic, Denmark, Finland, France,
Germany, Greece, Iceland, Ireland, Italy,
Luxembourg, Netherlands, Norway, Portugal,
Spain, Sweden, Switzerland and the United
Kingdom.

2 BSI 04-1999
 ISO 6326-3:1989 (E)

1 Scope The mixture consists of equal parts of

the pentasodium salt of diethylenetriamine pentaacetic acid
This part of ISO 6326 specifies a potentiometric (Na5DTPA);
method for the determination of hydrogen sulfide, the trisodium salt of N-hydroxyethylenediamine triacetic
acid (Na3HEDTA);
mercaptan sulfur, and carbonyl sulfide sulfur in
the sodium salt of N,N-di(2-hydroxyethyl-glycin) (NaDHEG);
natural gas in the concentration range equal to or the tetrasodium salt of ethylenediamine tetraacetic acid
above 1 mg/m3. The gas must be free of dust, mist, (Na4EDTA).
oxygen, hydrogen cyanide and carbon disulfide. The 4.2 Monoethanolamine, solution.
hydrogen sulfide/mercaptan sulfur ratio and also
Dissolve 5 g of monoethanolamine (C2H7ON) in 95 g
the mercaptan sulfur/hydrogen sulfide ratio should
of ethanol.
not exceed 50 : 1.
4.3 Nitrogen, purity better than 99,95 %,
The method is not recommended for gases
oxygen-free, under pressure.
containing more than approximately 1,5 % (V/V)
carbon dioxide. 4.4 Silver nitrate, standard volumetric solution,
NOTE In all parts of ISO 6326, 1 m3 of gas is expressed at c(AgNO3) 0,01 mol/l.
normal conditions (0 C; 101,325 kPa). For the preparation of the silver nitrate solution use
boiled distilled water, cooled to 20 C while bubbling
2 Normative references with nitrogen (4.3), to remove all traces of oxygen.
The following standards contain provisions which, Dissolve about 1,7 g of silver nitrate in 200 ml of
through reference in this text, constitute provisions water in the 1 000 ml one-mark volumetric
of this part of ISO 6326. At the time of publication, flask (5.6) and make up to the mark with water.
the editions indicated were valid. All standards are Standardize the solution with hydrochloric acid
subject to revision, and parties to agreements based [c(HCl) = 0,01 mol/l].
on this part of ISO 6326 are encouraged to 4.5 Ammonium hydroxide solution
investigate the possibility of applying the most (A20 C = 0,90 g/ml).
recent editions of the standards listed below.
Members of IEC and ISO maintain registers of 4.6 Electrolyte solution.
currently valid International Standards. Mix 1 000 ml of methanol and 25 ml of ammonium
ISO 385-1:1984, Laboratory glassware hydroxide solution (4.5).
Burettes Part 1: General requirements. 4.7 Cotton-wool, for the removal of dust.
ISO 648:1977, Laboratory glassware One-mark
pipettes. 5 Apparatus
ISO 1042:1983, Laboratory glassware One-mark Ordinary laboratory apparatus and
volumetric flasks. 5.1 Test apparatus, (see Figure 1), consisting of
three washing bottles (high-speed absorbers of any
3 Principle suitable design), maximum pore diameter 90 4m
Hydrogen sulfide and mercaptans are absorbed in to 150 4m; 1 washing bottle for the removal of dust,
a 35 % (m/m) aqueous potassium hydroxide solution if required; gas meter, wet design,
and carbonyl sulfide in a 5 % (m/m) ethanoholic tolerance 0,1 litre, with thermometer and water
monoethanolamine solution. The solutions are manometer. The thermometer shall have a
titrated potentiometrically using silver nitrate measuring range of 0 C to at least 30 C. The scale
solutions with a silver/silver sulfide electrode intervals shall be not less than 0,5 C.
system to indicate the end point. The connections between the three washing bottles
shall be glass to glass sealed by fluorelastomer
4 Reagents and materials tubing.
NOTE For low levels of sulfur compounds, butt connections and
During the analysis, use only reagents of recognized stop cocks with polytetrafluoroethylene plugs instead of the
analytical grade and only distilled water or water of screw clamps are recommended.
equivalent purity. 5.2 One-mark pipette, of capacity 10 ml, complying
4.1 Potassium hydroxide, solution. with ISO 648.
Dissolve 35 g of potassium hydroxide (KOH) in 65 g 5.3 Microburette, of capacity 10ml, complying
of water. with ISO 385-1.
NOTE In order to prevent interference by heavy metal 5.4 Beaker, of capacity 300 ml.
ions, 0,5 g of a mixture of polyaminoacetic acids is added for
each 50 ml of absorption solution to inactivate the heavy metal 5.5 Measuring cylinder, of capacity 50 ml.
ions. 5.6 One-mark volumetric flask, of capacity 1 000 ml,
complying with ISO 1042.

BSI 04-1999 3
ISO 6326-3:1989 (E)

5.7 High-resistance voltmeter, range 1 000 mV, The gas is passed through the absorption solutions
accuracy better than 5 mV. (An automatic at a flow rate of 120 l/h 20 l/h. Read the
titrimeter may be used, providing that it meets the temperature and pressure of the gas and the
above specification.) atmospheric pressure during the absorption period.
5.8 Silver/silver sulfide measuring electrode The amount of gas depends on the content of sulfur
compounds; 100 litres to 200 litres are sufficient in
NOTE Ion-selective silver/silver sulfide crystal membrane
electrodes are commercially available and allow faster and more
most cases.
precise titration, especially at low sulfur concentrations. If such Close the sampling valve (B) and read the amount
an electrode is not available, a conventional silver/silver sulfide of gas passed through the solutions on the gas
electrode may be prepared according to the following procedure.
Prepare a solution of sodium sulfide and sodium hydroxide by meter (G). By the free end of the T-piece,
dissolving 1,2 g of sodium sulfide nonahydrate (Na2S,9H2O) pass 10 litres of nitrogen (4.3) through the washing
and 40 g of sodium hydroxide in 1 litre of water. bottles to transfer the dissolved carbonyl sulfide
Clean the silver metal of the electrode with fine abrasive paper from the potassium hydroxide into the
and immerse it in 100 ml of the sodium sulfide/sodium hydroxide
solution, stir the solution and add 10 ml of the silver nitrate monoethanolamine solution. Close the washing
solution (4.4) over a period of 10 min to 15 min. Remove the bottles (E and F) hermetically and titrate the
electrode from the solution, wash it with water and wipe it lightly solutions containing the absorbed sulfur compounds
with a clean cloth. The coating should last for several weeks. immediately.
Before use, soak the electrode for at least 5 min in 100 ml of the
electrolytic solution (4.6) to which 0,5 ml of silver nitrate 7.3 Potentiometric titration
solution (4.4) has been added. Store the electrode in this solution.
7.3.1 Determination of hydrogen sulfide and
5.9 Silver/silver chloride reference electrode.
mercaptan sulfur
5.10 Electric stirrer.
Flush the 300 ml beaker (5.4) with nitrogen (4.3).
Quantitatively transfer the contents of the washing
6 Sampling
bottle (E) into the beaker and dilute with
On-line sampling is recommended. In the case approximately 200 ml boiled distilled water, cooled
where indirect sampling is indispensable, use to 20 C. While bubbling with nitrogen (4.3),
sampling cylinders in accordance with clause 3 of add 2 ml of concentrated ammonium hydroxide
ISO 6326-1:1989. solution (4.5) using the pipette (5.2).
CAUTION Ammonia must not be added
7 Procedure after the titration has commenced because of
7.1 Preliminary operations possible formation of explosive compounds.
Assemble the absorbers in series, as shown The dilution of the absorption solution is necessary
in Figure 1. to reach a fast response of the voltmeter (5.7).
Place 50 ml of potassium hydroxide solution (4.1) in Immerse the electrodes (5.8 and 5.9) in this mixture.
the washing bottle (E), and 50 ml of Start a nitrogen purge of the liquid surface and
monoethanolamine solution (4.2) in each of the two continue this throughout the titration. Stir the
washing bottles (F). In order to remove the oxygen solution with the electric stirrer (5.10). Start
dissolved in the absorption solutions, purge the titration as soon as a constant voltage is attained
assembly with nitrogen (4.3) for a period of 5 min (initial voltage). This condition is fulfilled if the
to 10 min, at a rate of 1 l/min to 2 l/min. voltage varies by less than 5 mV/min. For high
levels of sulfur compounds it is recommended to
Transfer the washing bottles, closed hermetically
with screw-clamps (D), to the sampling point titrate an aliquot part of the diluted absorption
and assemble the testing apparatus as shown solution while adding an appropriate amount of
ammonium hydroxide solution (4.5).
in Figure 1. If required, connect an additional
washing bottle filled with cotton-wool (4.7) between Carry out the titration with the standard volumetric
the sampling cock (B) and the T-piece (C) to silver nitrate solution (4.4), initially in steps
intercept any solid particles. of 0,5 ml. The tip of the microburette shall be
immersed about 20 mm in the solution during the
7.2 Absorption (see Figure 1)
entire titration process. Measure the voltage after
Flush the sampling line and the T-piece (C) with adding each 0,5 ml of silver nitrate solution.
gas. Open the screw-clamps (D) at the inlet and Resume the titration after a constant voltage is
outlet of the washing bottles (E and F) and record attained. 5 min to 10 min may elapse before an
the initial reading of the gas meter (G). unchanging potential is attained.

4 BSI 04-1999
 ISO 6326-3:1989 (E)

Figure 1 Test apparatus

If, after each addition of silver nitrate solution, the 7.3.3 Graphic presentation of titration curves
voltage varies by more than 10 mV, reduce the Plot the volumes of standard volumetric silver
volumes of silver nitrate solution added from 0,5 ml nitrate solutions used against the voltages
to 0,1 ml and from 0,1 ml to 0,05 ml. Continue the measured, on a coordinate system. Determine
titration until the change of the voltage is less the end points for hydrogen sulfide
than 5 mV for 0,1 ml of solution and the voltage (approximately 320 mV) and for mercaptan
exceeds + 200 mV. Then record the voltage and sulfur (approximately + 100 mV), on the titration
microburette reading. curve obtained according to 7.3.1 and record the
NOTE The voltage depends on the electrode combination. The corresponding volume of silver nitrate solution
values given should be regarded as approximative values.
used. The potentials may vary with different makes
7.3.2 Determination of carbonyl sulfide sulfur of instruments.
Quantitatively transfer the absorption solutions in Figure 2 shows a typical titration curve.
the washing bottles (F) to the beaker (5.4) and Titration in accordance with 7.3.2 should show a
add 50 ml of the electrolyte solution (4.6). Carry out similar curve with only one end point.
the titration as described in 7.3.1. The initial
voltage may be 350 mV. The titration should be 8 Expression of results
continued to a final voltage of + 100 mV. Since the
intermediate voltages are attained very slowly, 8.1 Method of calculation
several minutes will be required, especially at the The mass concentration of hydrogen sulfide A(H2S),
end of the titration, after each addition of the silver expressed in milligrams per cubic metre, is given by
nitrate solution (4.4). the equation
CAUTION To avoid accidents due to the
formation of highly explosive silver fulminate, 17 cV1
A( H 2 S ) = ------------------
-
the solution must be disposed of immediately Vn
after titration is completed.
NOTE The voltage depends on the electrode combination. The
values given should be regarded as approximative values.

BSI 04-1999 5
ISO 6326-3:1989 (E)

Vn is the total volume, in cubic metres, of dry gas

analysed at normal conditions:
VT n ( pamb + p e p D )
Vn = ------------------------------------------------------------
-
pn T
V is the volume of the gas sample measured
according to 7.2 at temperature T (kelvins) and
pressure p (kilopascals):
p = pamb + pe pD
Tn is the thermodynamic temperature, in
kelvins, at normal conditions (273,15 K);
T is the thermodynamic temperature, in kelvins,
of the gas sample;
pn is the pressure, in kilopascals, at normal
conditions (101,325 kPa);
Figure 2 Example of a titration curve pamb is the atmospheric pressure, in kilopascals,
(see 7.3.3)
measured during gas sampling;
The mass concentration of mercaptan pe is the excess pressure, in kilopascals,
sulfur A(S-RSH), expressed in milligrams per cubic measured with the water manometer during gas
metre, is given by the equation sampling;
32 cV pD is the partial pressure of water vapour, in
A( S-RSH ) = ------------------2- kilopascals, in the gas meter at T (kelvins).
Vn
The mass concentration of carbonyl sulfide sulfur Round the results to the nearest 0,1 mg/m3.
A(S-COS), expressed in milligrams per cubic metre, 8.2 Precision
is given by the equation The precision of the method, as obtained by
16 cV statistical examination of interlaboratory test
A ( S-COS ) = ------------------3- results, is as follows.
Vn
8.2.1 Repeatability
where
The difference between two test results, obtained by
c is the actual concentration, in moles per litre, of the same operator with the same apparatus under
standard volumetric silver nitrate solution (4.4) constant operating conditions on identical test gas
used [c(AgNO3) 0,01 mol/l]; would, in the long run, in the normal and correct
V1 is the volume, in millilitres, of standard operation of the test method, exceed the values
volumetric silver nitrate solution (4.4) used in given in Table 1 in only one case out of twenty.
titrating to the first inflexion in the curve 8.2.2 Reproducibility
(corresponding to the mass concentration of
The difference between two single and independent
hydrogen sulfide) (see Figure 2);
results, obtained by different operators working in
V2 is the volume, in millilitres, of standard different laboratories on identical test gases would,
volumetric silver nitrate solution (4.4) added in in the long run, in the normal and correct operation
titrating between the first and second inflexions of the test method, exceed the values given in
in the curve (corresponding to the mass Table 1 in only one case out of twenty.
concentration of mercaptan sulfur)
(see Figure 2); 9 Test report
V3 is the volume, in millilitres, of standard The test report shall include the following
volumetric silver nitrate solution (4.4) added to information:
reach the end point (corresponding to the mass a) a reference to this part of ISO 6326;
concentration of carbonyl sulfide sulfur), in
accordance with 7.3.2; b) all information necessary for the complete
identification of the sample (e.g. type and
identification of the gas tested and the date of
sampling);
c) the sampling method used;

6 BSI 04-1999
 ISO 6326-3:1989 (E)

d) the results and the method of calculation used;

e) details of any deviation from the procedure
specified in this part of ISO 6326 or any
circumstance that may have influenced the
results.
Table 1 Precision data
Concentration range Repeatability Reproducibility
mg/m3 % %
A(H2S): 1 to 10
15 20
A(S-RSH): 1 to 20
A(S-COS): 1 to 30 10 15

BSI 04-1999 7
8 blank
 BS EN ISO 6326-3:1998

List of references

See national foreword.

BSI 04-1999
BS EN ISO
6326-3:1998
BS BSI British Standards Institution
3156-11.4.3:
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