uop

HYDROGEN SULFIDE, MERCAPTAN SULFUR,

AND CARBONYL SULFIDE
IN HYDROCARBON GASES
BY POTENTIOMETRIC TITRATION
UOP Method 212-05
SCOPE
This method is for determining hydrogen sulfide (H2S), mercaptan sulfur (RSH) and carbonyl
sulfide (COS) in gaseous hydrocarbons and in typical liquefied petroleum gas (LPG) consisting of C3
and/or C4 hydrocarbons. Also covered is the determination of mercaptan sulfur in LPG which may
contain a wide range of hydrocarbon types ranging from ethane to such gasoline boiling range
hydrocarbons as pentane and hexane. Each sulfur type can be determined from less than 1 to several
thousand mass-ppm sulfur (less than 0.1 to several thousand grains per 100 cu ft).

REFERENCES
ASTM Method D 1070, Relative Density of Gaseous Fuels, www.astm.org
ASTM Method D 6667, Total Volatile Sulfur in Gaseous Hydrocarbons and Liquefied Petroleum
Gases by Ultraviolet Fluorescence, www.astm.org
Bruss, D.B., Wyld, G.E.A., and Peters, E.D., Anal. Chem., 29, 807 (1957)
Handbook of Chemistry and Physics; www.crcpress.com
Lykken, L., and Tuemmler, F.D., Ind. Eng. Chem., Anal. Ed., 14, 67 (1942)
Tamele, M.W., Ryland, L.B., and Irvine, V.C., Ind. Eng. Chem., Anal. Ed., 13, 618 (1941)
UOP Method 163, Hydrogen Sulfide and Mercaptan Sulfur in Liquid Hydrocarbons,
www.astm.org
UOP Method 516, Sampling and Handling Gasolines, Distillate Fuels, and of C3-C4 Fractions,
www.astm.org
UOP Method 948, Relative Density of Gas Mixtures by Calculation from Composition,
www.astm.org
UOP Method 999, Precision Statements in UOP Methods, www.astm.org
IT IS THE USER'S RESPONSIBILITY TO ESTABLISH APPROPRIATE PRECAUTIONARY PRACTICES AND TO
DETERMINE THE APPLICABILITY OF REGULATORY LIMITATIONS PRIOR TO USE. EFFECTIVE HEALTH AND
SAFETY PRACTICES ARE TO BE FOLLOWED WHEN UTILIZING THIS PROCEDURE. FAILURE TO UTILIZE THIS
PROCEDURE IN THE MANNER PRESCRIBED HEREIN CAN BE HAZARDOUS. MATERIAL SAFETY DATA SHEETS
(MSDS) OR EXPERIMENTAL MATERIAL SAFETY DATA SHEETS (EMSDS) FOR ALL OF THE MATERIALS USED IN
THIS PROCEDURE SHOULD BE REVIEWED FOR SELECTION OF THE APPROPRIATE PERSONAL PROTECTION
EQUIPMENT (PPE).
COPYRIGHT 1959, 1968, 1972, 1977, 2003, 2004, 2005 UOP LLC. All rights reserved.
Nonconfidential UOP Methods are available from ASTM International, 100 Barr Harbor Drive, PO Box C700, West
Conshohocken, PA 19428-2959, United States. The UOP Methods may be obtained through the ASTM website,
www.astm.org, or by contacting Customer Service at service@astm.org, 610.832.9555 FAX, or 610.832.9585 PHONE.

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OUTLINE OF METHOD
The sample, taken either from a sample cylinder or directly from a refinery stream according to the
procedures described in UOP Method 516, is scrubbed first through a potassium hydroxide solution
and then through a monoethanolamine solution. The potassium hydroxide solution contains chelating
agents which inhibits the oxidation of sulfur compounds by chelating heavy metals. A potentiometric
titration of the absorbed hydrogen sulfide and mercaptan sulfur in the potassium hydroxide solution
follows, using either an aqueous or an alcoholic silver nitrate titrant. The monoethanolamine
solution, which contains the absorbed carbonyl sulfide is titrated potentiometrically with alcoholic
silver nitrate in an acidic titration solvent. The electrode system for both titrations is a silver/silver
sulfide electrode with a glass reference electrode. The concentration of each analyzed component is
calculated from the titration curve. Either an automatic (preferred) or a manually-operated titrator
may be used.

APPARATUS
References to catalog numbers and suppliers are included as a convenience to the method user.
Other suppliers may be used if equivalent performance can be obtained.
In addition to the apparatus listed below, all of the sampling-related apparatus specified in UOP
Method 516 for C3-C4 fractions is also required for this method.
Balance, capable of weighing 5 kg to the nearest 0.5 g
Balance, readability 0.1-mg
Barometer, Fisher Scientific, Cat. No. 02-406
Beakers, electrolytic, 250-mL, Brinkmann Instruments, Cat. No. 020212209, two or more required
Beaker, stainless steel, 4000-mL, Fisher Scientific, Cat. No. 02-583G. Drill a hole in the bottom to
fit the selected neoprene stopper.
Cleaning pad, synthetic, mildly abrasive, Scotch-Brite, Runco Office Supply, Cat. No. MMM-96
Electrode, combination silver/glass titrode, Brinkmann Instruments, Cat. No. 020948507. The
electrode should be dedicated to sulfur analysis.
Flasks, volumetric, Class A, 250-, 500-, and 1000-mL, Fisher Scientific, Cat. Nos. 10-210-5E, -5F,
and -5G, respectively
Flask, volumetric, Class A, amber, for light sensitive materials, 100-mL, Fisher Scientific, Cat. No.
10-229C
Funnel, separatory, 250-mL, Fisher Scientific, Cat. No. 10-437-5C
Gas washing bottle, 125-mL. The type fitted with sintered glass disk of coarse porosity is suitable
and can be obtained commercially, Reliance Glass, Cat. No. LG-3761-100, or, Fisher Scientific,
Cat. No. 03-040A. Because light is the most serious factor affecting recovery of carbonyl sulfide,
completely mask the gas washing bottle with black tape. In order to view the bubbling, a vertical
slit, 2-3 mm wide, may be cut in the tape, which can taped over except when needed.
Gas washing bottle, 250-mL, Reliance Glass, Cat. No. LG-3690-110
Gas washing bottles, 250-mL. The type fitted with a sintered glass gas-distribution plate of coarse
porosity is suitable and this type can be obtained commercially, Reliance Glass, Cat. No. LG212-05

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3762-102, or Fisher Scientific, Cat. No. 03-040B, two required. The maximum gas flow rate for
this type of gas washing bottle is about 30 L/hr (1 cu ft/hr).
If no COS scrubber is connected downstream of the caustic scrubbers, an alternative gas washing
bottle, suitable for a higher flow rate, may be used. This type is fitted with a perforated disk gas
distributor (see Figure 1), and is available on special order from Reliance Glass. The rate with
this distributor can be as high as 90 L/hr (3 cu ft/hr), provided that no COS scrubber is connected
downstream from the caustic scrubber. The scrubbing rate for the COS scrubber must not exceed
30 L/hr.

Gauge, pressure, stainless steel, 0 to 2800 kPa gauge (0 to 400 psig) range, Matheson Tri-Gas, Cat.
No. 63-2242, with adapter to fit the specific sample cylinders used
Graduated cylinders, 5-, 100-, and 1000-mL, Fisher Scientific, Cat. No. 08-550A, -550E, and 550H, respectively
Laboratory expansion valve, Swagelok Type SS-3NRS4 (regulating stem 316 stainless steel valve
and fittings), Swagelok. Wrap the valve with electrical heating tape and provide a variable
transformer to control the temperature of the tape. (See Figure 2 for laboratory expansion valve
apparatus arrangement.) To ensure that the valve provides a smooth, regular flow without any
blockages, it must be cleaned regularly, by rinsing with water,. Additional maintenance requires
either a rebuild kit, returning to the manufacturer for repair, or replacement.

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Pipets, Class A, 1-, 2-, 3-, 5-, 10-, 15-, 25-, and 50-mL, Fisher Scientific, Cat. Nos. 13-650-2B, -2C,
-2D, -2F, -2L, -2M, -2P, and -2S, respectively
Pipet, Mohr, 5-mL, Fisher Scientific, Cat. No. 13-665K
Pipet filler, Fisher Scientific, Cat. No. 03-692-35
Refinery expansion valve, Swagelok Type SS-3NRS4 (regulating stem 316 stainless steel valve and
fittings), Swagelok. Since the use of electrically-heated expansion valves is not permitted in
refineries, use a hot water heating system for vaporizing an on-stream sample. (See Figure 3 for
refinery expansion valve apparatus arrangement.) To ensure that the valve provides a smooth,
regular flow without any blockages, it must be cleaned regularly, by rinsing with water.
Additional maintenance requires either a rebuild kit, returning to the manufacturer for repair, or
replacement.
Regulator, nitrogen, two-stage, high-purity, delivery pressure range 15-200 kPa (2-30 psi),
Matheson Tri-Gas, Model 3121-580
Stoppers, neoprene, sizes to fit specific apparatus. Fisher Scientific, Cat. No. 14-141*. Bore holes
as necessary using Boring Machine, Fisher Scientific, Cat. No. 07-855. *Select sizes to fit
containers.
Stopwatch, Fisher Scientific, Cat. No. 14-648-3
Tape, heating, electrical, Fisher Scientific, Cat. No. 11-463-54A
Tape, polyethylene, black, Fisher Scientific, Cat. No. 11-866-2
Thermometer or thermocouple, capable of reading heated expansion valve temperature of 38-43C
(100-110F)
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Titrator, potentiometric, recording, 2000-mV range, 1-mV resolution, capable of reducing the
titration rate to a minimum in the vicinity of the endpoint, with dispenser having a volume
readout of 0.00 - 99.99 mL, 0.0001 of the buret volume resolution, Metrohm Model 836 Titrando
system with optional sample changer, and 20-mL buret, Brinkmann Instruments
Transformer, variable, Fisher Scientific, Cat. No. 11-472-76 (for 120V)
Tubing, rubber, 3/16 ID, Fisher Scientific, Cat. No. 14-167C
Tubing, stainless steel, OD, Alltech Associates, Cat. No. 30306ST
Wash bottle, for 2-propanol, Fisher Scientific, Cat. No. 03-409-20D
Wet test gas meter or calibrated gas receiver, 225 L/hr capacity, Meters & Controls, American
Meter, Cat. No. AL 17-1. An equivalent meter, calibrated in cu ft, is available as Cat. No. AL
17, see APPENDIX.

REAGENTS AND MATERIALS

References to catalog numbers and suppliers are included as a convenience to the method user.
Other suppliers may be used. References to water mean double deionized or distilled water purged
with nitrogen for 10 to 15 minutes before use to remove dissolved oxygen. Unqualified references to
solutions mean aqueous solutions.
In addition to the reagents and materials listed below, the reagents and materials specified in UOP
Method 516 for C3-C4 fractions are also required for this method.
Acetic acid, glacial, Certified ACS Plus, Fisher Scientific, Cat. No. A38-212

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Acid titration solvent. Dissolve 2.7 g of sodium acetate trihydrate in 20 mL of water and 975 mL of
anhydrous ethyl alcohol. Add 4.6 mL of glacial acetic acid to the solution. Purge the solution
with nitrogen for 10 to 15 minutes prior to use to remove dissolved oxygen.
Ammonium hydroxide, concentrated, Certified ACS Plus, Fisher Scientific, Cat. No. A669-212
Cadmium chloride, Certified ACS, Fisher Scientific, Cat. No. C10-500
Cadmium chloride solution. Dissolve 100 g of cadmium chloride in 500 mL of water. Add 10 mL
of concentrated hydrochloric acid and make up to a final volume of 1 L with water. Purge with
nitrogen for 10 to 15 minutes before using.
Chelating solution, a solution of chelating agents found effective in reducing the deterioration of
sulfides and mercaptides in caustic solutions. The recommended usage is 2 mL/100 mL of caustic
solution. This chelating solution is made up from the constituent chemicals:

Diethylenetriamine pentaacetic acid, sodium salt (Na5DTPA), Acros Organics, Fisher

Scientific, Cat. No. 40729-0010 (40% aqueous solution)
Diethylenetriamine pentaacetic acid, sodium salt, 20 mass-% solution. Dilute diethylenetriamine pentaacetic acid, sodium salt, 40% aqueous solution, with water to make a 20 mass% solution.
N-(2-hydroxyethyl) ethylenediaminetriacetic acid, sodium salt, (Na3HODTA), Aldrich, Cat.
No. 16,153-5, or Acros Organics, Fisher Scientific, Cat. No. 34870-0010
N-(2-hydroxyethyl) ethylenediaminetriacetic acid, sodium salt, 20 mass-% solution. Dissolve
N-(2-hydroxyethyl) ethylenediaminetriacetic acid, sodium salt, in water to make a 20 mass-%
solution.
Ethylenediaminetetraacetic acid, sodium salt (Na4EDTA), Aldrich Chemical, Cat. No. E2,6290, or, Acros Organics, Fisher Scientific, Cat. No. 14786-5000
N,N-bis(2-hydroxyethyl)glycine (Bicine), Aldrich Chemical, Cat. No. 16,379-1, or, Acros
Organics, Fisher Scientific, Cat. No. 17265-1000
Mix 1:1 by weight ethylenediaminetetraacetic acid, sodium salt, and N,N-bis(2-hydroxyethyl)
glycine. Dissolve in water to make a 20 mass-% solution. Mix equal volumes of each of the
three 20 mass-% solutions to make the final chelating solutiuon.
Detergent, LiquiNox, Fisher Scientific, Cat. No. 04-322-15B
Ethyl alcohol, anhydrous, spectro grade, Acros Organics, Cat. No. 22409-5000
Hydrochloric acid, concentrated, Certified ACS Plus, Fisher Scientific, Cat. No. A144S-500
Lead acetate test paper, Fisher Scientific, Cat. No. 14-862
Leak test solution, soap solution, Snoop, Swagelok, Cat. No. MS-SNOOP-8OZ
Monoethanolamine (ethanolamine), 99%, Acros Organics, Cat. No. 14958-0025
Monoethanolamine, 5 vol-% solution in ethyl alcohol. Prepare by pipetting 5 mL of
monoethanolamine into an amber 100-mL volumetric flask. Fill to the mark with ethyl alcohol.
Store in a dark place. Purge with nitrogen for 10 to 15 minutes before using. Discard after one
day.
Nitrogen, high purity, 99.99%
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Potassium hydroxide, 50 w/v-% solution, Fisher Scientific, Cat. No. LC19260-2

Potassium hydroxide, 40 w/v-% solution. Prepare by diluting four parts of 50 w/v-% solution with
one part of water. Purge with nitrogen for 10 to 15 minutes before using. Use only for samples
high in hydrogen sulfide.
Potassium hydroxide, 10 w/v-% solution, Fisher Scientific, Cat. No. LC19200-2
nitrogen for 10 to 15 minutes before using.

Purge with

2-Propanol, Certified ACS grade, Fisher Scientific, Cat. No. A416-4. Purge with nitrogen for 10 to
15 minutes before using.
Silver nitrate, 0.1-M solution, standardized at 25C against NIST potassium chloride, lot analysis
supplied, Fisher Scientific, Cat. No. SS72-4
Silver nitrate, 0.01-M standard aqueous solution. Prepare by pipetting 50 mL of the 0.1-M solution
into a 500-mL volumetric flask. Dilute to the mark with water, cap and invert several times to
mix thoroughly. The molarity of this solution is one-tenth the molarity of the purchased,
nominally 0.1-M solution.
Silver nitrate, 0.01-M standard alcoholic solution. Prepare by pipetting 50 mL of the 0.1-M solution
into a 500-mL volumetric flask. Dilute to the mark with 2-propanol, cap and invert several times
to mix thoroughly. The molarity of this solution is one-tenth the molarity of the purchased,
nominally 0.1-M solution.
Sodium acetate trihydrate, Certified ACS grade, Fisher Scientific, Cat. No. S209-500
Sodium carbonate, 5 w/v-% solution, Fisher Scientific, Cat. No. LC22970-2. Purge with nitrogen
before using.
Sodium hydroxide, 20 w/v-% solution, Fisher Scientific, Cat. No. LC24090-2
Sodium sulfide, 3 w/v-% solution, Fisher Scientific, Cat. No. LC24920-2
Wipers, Kimwipes, Ex-L, Fisher Scientific, Cat. No. 06-666A

SAMPLING
Refer to UOP Method 516, Sampling and Handling of Gasolines, Distillate Fuels, and C3-C4
Fractions, for the required sample cylinders (Silcosteel recommended), their preparation and cleaning,
and sampling procedures for C3-C4 fractions.

SCRUBBING OF GASES
If analysis of COS is not required, the COS scrubber may be eliminated, and, if desired, scrubbers
with perforated disk distributors may be used at the higher flow rate. In CALCULATIONS, it is
assumed that the gas is saturated with water when metered. For greatest accuracy, it is advisable to
provide a water saturator between the last scrubber and the meter.
Scrubbing in the Laboratory
CAUTION: This method involves venting a pressurized cylinder into vessels containing a caustic
solution. The pressure in the LPG cylinder should be checked with a pressure gauge prior to
scrubbing to ensure that the cylinder is under LPG vapor pressure only. Additional pressure may
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deliver too high a flow rate into the caustic scrubbing solution and cause splashing. Also see NOTES
AND PRECAUTIONS.

Special care should be taken when handling the LPG during the scrubbing procedure to avoid caustic
splashing. Use a face shield during the scrubbing procedure.

All scrubbing operations should include the use of the chelating solution, 2 mL for each 100 mL of
potassium hydroxide, in order to reduce the deterioration of sulfides and mercaptides in caustic
solutions.
Scrubbing in a laboratory is carried out by mounting the sample cylinder and adapter (consisting of
connecting lines, expansion valve, and stainless steel tubing) vertically over the scrubber and
connecting it as shown in Figure 2.
1. Equip the first scrubber with a 2-hole neoprene stopper. One hole is to accept the stainless steel
tubing on the sample cylinder and the other is for the stainless steel tubing vent into the next
scrubber in the train.
2. Place the appropriate solutions in the gas washing bottles of the scrubbing train. See following
sections for specific solutions for each application.
3. Connect the last scrubber to a wet test meter to measure the volume and rate of scrubbing.
Vent the flow out of the wet test meter into a hood or other safe area.

Use a minimum length of rubber tubing for all connections, consistent with being able to connect the inlet
and the outlet of a scrubber with one piece of rubber tubing to maintain a closed system.

4. Purge the connected scrubbers with nitrogen for 10 min.

5. Mount the adapter vertically above the first scrubber.
6. Place the LPG sample cylinder in a vertical position in a hood or well-vented area. If the
cylinder has an outage tube, the outage tube must be at the top. Attach the gauge to the valve at
the top of the cylinder and check the pressure in the cylinder. See NOTE 1. Briefly open the
bottom valve (A) to check that no water or sediment is present in the LPG. If water or sediment
is determined to be present, discontinue the analysis and obtain a clean sample.

LPG samples are usually contained in a cylinder having valves on both ends or, in some cases, a
cylinder where one of the valves is connected to an eductor tube. If the sample cylinder contains an
eductor tube, invert the cylinder (both valves on the bottom) and briefly open the valve not connected to
the eductor tube to check that no water or sediment is present.

7. Weigh the sample cylinder to the nearest 0.5 g.

8. Position the cylinder directly over the adapter and connect it to the adapter. Pass the stainless
steel tubing through the remaining hole in the neoprene stopper to a depth of 1 cm from the
bottom of the scrubber.
9. Turn on the power to the heating tape and adjust the transformer so that the temperature of the
gas expansion valve is 38-43C.
10. Record the initial wet test meter readings (L) as well as the wet test meter temperature (C) and
the atmospheric pressure (mbar).
11. Ensure that the gas expansion valve is fully closed.
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12. Open the lower valve of the sample cylinder all the way. Check for leaks at the fittings using
the leak test solution.
13. Slowly open the gas expansion valve and start the flow of sample through the scrubber and wet
test meter. Adjust the flow of gas so as not to exceed 30 L/hr (1.5 L in 3 minutes). (Excess flow
can cause the caustic scrubbing solution to splash). If the gas washing bottles are of the type
fitted with a perforated disk gas distributor, and no COS scrubber is connected downstream
from the caustic scrubber, the rate can be as high as 90 L/hr.
14. After the appropriate volume of sample has been scrubbed, turn off the heat and close the lower
valve of the sample cylinder.
15. After gas bubbles cease to come out of the tip of the adapter, disconnect the adapter from the
cylinder. Raise the adapter just high enough so that its tip is out of the scrubber solution and
wash the inside of the adapter with about 5 ml of water, collecting the washings in the scrubber
solution.
16. Remove the adapter from the scrubber and disconnect the vent line to the next scrubber. Cap
the first scrubber with a neoprene stopper. Disconnect the remaining scrubbers and quickly
connect the inlet of each scrubber to its own outlet with the rubber tubing used to connect the
scrubbers, thus minimizing exposure to air.
17. Record the volume of the gas metered. Reweigh the sample cylinder to the nearest 0.5 g to
determine the weight of sample scrubbed (see NOTES AND PRECAUTIONS).
Scrubbing in the Refinery
Scrubbing in the refinery follows the same procedures as scrubbing in the laboratory except for the
following changes. When the scrubbing of a gas or LPG sample is to be carried out in a refinery, an
electrically-heated expansion valve cannot be used because of the danger of explosion. Therefore, an
expansion valve heated by warm water is employed. Figure 3 shows the vaporization apparatus used
in on-stream scrubbing at the refinery. Follow all applicable refinery safety practices, modifying the
apparatus and procedure if necessary.
The heat necessary to warm the water is supplied by refinery steam lines. A cold-water jacket,
located upstream of the expansion valve, is necessary when using warm water to heat the expansion
valve in order to avoid conductive heating of the line upstream from the valve. The cold water for the
cooling jacket is supplied by the refinery water lines. Determine the weight of the sample from the
volume of gas scrubbed as measured by the wet test meter. Vent the meter in a safe area.
The following sample types (A through D) are typical of those found in various refinery streams.
Procedures can be modified for other sample types as necessary.
Samples Containing Relatively High Hydrogen Sulfide and Carbonyl Sulfide
Concentrations, and Low Mercaptan Concentration (Sample Type A)
For such samples as gases from catalytic cracking that contain in excess of 1000 ppm of hydrogen
sulfide and some carbonyl sulfide, more concentrated solution of potassium hydroxide is required.
The low (less than 100 ppm) mercaptan concentration is typically not measured. If it is necessary to
measure the low mercaptan concentration, repeat the analysis using the procedure in Sample Type C.
1. Place 50 mL of 40 w/v-% potassium hydroxide solution and 1 mL of the chelating solution into
each of two 250-mL scrubbers and mix by swirling.
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The chelating solution is required to prevent loss of sulfide.

2. Place 20 mL of 5 vol-% alcoholic monoethanolamine solution into the third scrubber (125-mL),
which has been masked in black tape to exclude light.
3. Scrub about 60 L (2 cu ft) of gas.
4. Titrate the monoethanolamine scrubber solution as soon as possible after a sample has been
scrubbed (see PROCEDURE). Combine the two potassium hydroxide scrubber solutions and
titrate the same day (see PROCEDURE).
Samples Containing Relatively Low Hydrogen Sulfide, Mercaptan, and Carbonyl
Sulfide Concentrations (Sample Type B)
For purposes of this method, low concentrations of sulfur types are generally considered to be less
than 100 ppm.
1. Place 100 mL of 10 w/v-% potassium hydroxide solution and 2 mL of the chelating solution
into each of two 250-mL scrubbers and mix by swirling.
2. Place 50 mL of 5 vol-% alcoholic monoethanolamine solution into the third scrubber (125-mL),
which has been masked in black tape to exclude light.
3. Scrub about 300 L (10 cu ft) of gas.
4. Titrate the monoethanolamine scrubber solution as soon as possible after a sample has been
scrubbed (see PROCEDURE). Combine the two potassium hydroxide scrubber solutions and
titrate the combined solution the same day (see PROCEDURE).
Samples Containing Carbonyl Sulfide, Relatively High
Concentrations of Hydrogen Sulfide, and Low Concentrations of Mercaptan Sulfur
(Sample Type C)
For purposes of this method, high concentrations of sulfur types are generally considered to be
greater than 1000 ppm, and low concentrations of sulfur types are generally considered to be less than
100 ppm.
Mercaptan analysis: In some cases, samples will have a high ratio of hydrogen sulfide to mercaptan
sulfur. Where this condition exists, the accuracy of the mercaptan sulfur determination may be
affected adversely if additional scrubbers are not placed in the sampling train before the potassium
hydroxide scrubbers.
1. Charge the first 250-mL scrubber downstream from the expansion valve with 100 mL of 5 w/v% sodium carbonate solution. Charge the second 250-mL scrubber with 100 mL of 5 w/v-%
sodium carbonate solution.
2. Follow these 2 scrubbers with an empty scrubber which serves as a knockout trap, then follow
with two 250-mL gas scrubbers each containing 50 mL of 40 w/v-% potassium hydroxide
solution and 1 mL of chelating solution.
3. Scrub approximately 300 L (10 cu ft) of the gas.

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4. Combine the two potassium hydroxide scrubber solutions and titrate the combined solution the
same day as described in the PROCEDURE.
A separate analysis must be carried out to determine the respective concentrations of hydrogen
sulfide and carbonyl sulfide in samples of this type. The sampling procedure is identical to that
described previously for gases which are relatively high in hydrogen sulfide (Sample type A).
Samples Containing Mercaptan Sulfur Only and Appreciable
Concentrations of Pentane and Higher Boiling Materials (Sample Type D)
For purposes of this section, appreciable concentrations of pentane and higher boiling materials
are indicated when, after the scrubbing is complete, there is at least a 5-10 mL hydrocarbon layer
present in the scrubber.
1. Place 100 mL of 10 w/v-% potassium hydroxide solution and 2 mL of the chelating solution in
each of two 250-mL scrubbers and mix by swirling.
2. Scrub about 60 L (2 cu ft) of gas.
3. If there is a hydrocarbon layer present in the scrubber after sampling, remove the hydrocarbon
layer by using a nitrogen-purged separatory funnel.
4. Return the aqueous portion to the scrubber and replace the bubbler to exclude air.
5. Analyze the hydrocarbon phase for mercaptan sulfur using UOP Method 163. Use the entire
weight of sample scrubbed as the sample weight in the calculation of mercaptan sulfur in
accordance with UOP Method 163.
6. Titrate the aqueous phase as described in the PROCEDURE.
7. Sum the results of the titration and U163 to obtain the total mercaptan content.

PROCEDURE
The analyst is expected to be familiar with general laboratory practices, the technique of titration,
and with the equipment being used.
Caustic solutions containing sulfur compounds are quite susceptible to oxidation in air. The
solutions should, therefore, be protected by blanketing with nitrogen or other inert gas. Titrate
solutions immediately after they are ready.
Silver/Glass Electrode Preparation and Reconditioning
Proper electrode preparation is essential to obtain reproducible and noise-free titration curves
having good endpoints. When in use, the electrode should be reconditioned on a weekly basis. An
electrode should be dedicated to sulfur analysis. If it is used for any other titrations, it must be
reconditioned before use. Prepare and recondition the silver-silver sulfide electrode as follows:
1. Clean the silver surface with a cleaning pad. Rinse with water and dry.
2. Immerse the electrodes in a solution containing 100 mL of 2-propanol, 1 mL of ammonium
hydroxide, and 3 mL of 3 w/v-% sodium sulfide solution.

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3. While stirring at a moderate speed, slowly add approximately 10 mL of 0.01-M silver nitrate
solution over a period of 10 minutes. A film of silver sulfide will be deposited on the silver
electrode.
4. Wipe the excess silver sulfide from the electrode with a wiper.

The electrode should be cleaned after each titration by rinsing with water.

Hydrogen Sulfide and Mercaptans

1. Prepare the titrator for operation according to the instrument manufacturers instructions, with
the specified electrode in place and 0.01-M silver nitrate as the titrant.

Alcoholic silver nitrate may also be used for the sulfide and mercaptide titration to avoid changing titrant
for the carbonyl sulfide titration.

2. Check the contents of the caustic scrubbers qualitatively using lead acetate paper. If there is no
perceptible coloration of the paper, transfer the contents of the scrubbers into a 250-ml
electrolytic beaker. Proceed with Step 3. If the lead acetate paper shows any coloration,
quantitatively transfer the contents of the caustic scrubbers into a 250-ml volumetric flask.
Proceed with Step 4.
3. Wash the scrubbers (bottles and bubblers, not the rubber hose) with water and add the washings
to the same beaker. Add approximately 1 mL of concentrated ammonium hydroxide. Proceed
with Step 6.
4. Wash the scrubbers (bottles and bubblers, not the rubber hose) with water and add the washings
to the volumetric flask. Dilute to volume with water and mix by swirling. Again, check the
diluted solution with lead acetate paper and use Table 1 as a guide in selecting the proper
aliquot size.

Caustic solutions containing high levels of mercaptide and low levels of sulfide are titrated separately for
the two components. A sample is titrated as above to the mercaptide endpoint, and then a larger sample
is titrated only to the sulfide endpoint. The mercaptide concentration is determined by difference.

If the ratio of sulfide sulfur to mercaptide sulfur is greater than 10:1, then the mercaptide result is
considered to be qualitative.

Table 1
Selection of Aliquot Size
Color of lead acetate paper after
testing the diluted scrubber solution
dark brown
brown
light brown

Aliquot to be taken for

titration, mL
1 to 5
5 to 20
20 to 50

5. Pipet an aliquot into an electrolytic beaker. Add approximately 1 mL of concentrated

ammonium hydroxide. Dilute to about 50 mL with water.
6. Titrate with 0.01-M silver nitrate, automatically or manually (see Manual Titration) depending
on the equipment available.
Figure 4 shows three typical titration curves for samples containing mercaptan only, hydrogen
sulfide only, and both mercaptan and hydrogen sulfide in the same sample. Samples containing only
mercaptan will show an inflection in their titration curves at about 0.0 to +0.3V (Curve A). Samples
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containing only hydrogen sulfide will show an inflection in their titration curves at about -0.4 to
+0.2V (Curve B). When both hydrogen sulfide and mercaptan are present, 2 inflections (Curve C)
will be seen. The first inflection, at about -0.4 to -0.2V. indicates hydrogen sulfide and the second, at
about 0.0 to +0.3V, indicates mercaptan.
Mercaptans Only
1.

Prepare the titrator in the same manner as for the sulfide and mercaptan titration.

2.

Transfer the caustic scrubber solution from each of the two scrubbers to two separate 250-mL
electrolytic beakers. Wash each scrubber (bottles and bubblers, not the rubber hose) with 50
mL of water and add the water washings to each respective beaker. Add approximately 1 mL
of concentrated ammonium hydroxide to each of the two beakers.

3.

Using 0.01-M silver nitrate as the titrant, titrate automatically or manually (see Manual
Titration) depending on the equipment available.

Figure 4 shows a typical titration curve for samples containing only mercaptan sulfur (Curve A).

Carbonyl Sulfide
1.

Prepare the titrator in the same manner as for the sulfide and mercaptide titration.

2.

Transfer the monoethanolamine scrubber solution to an electrolytic beaker. Wash the

scrubber (bottle and bubbler, not the rubber hose) with two 50-mL portions of the acid
titration solvent and add the washings to the electrolytic beaker.
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3.

Using 0.01-M alcoholic silver nitrate, titrate automatically or manually (see Manual
Titration) depending on the equipment available.

Figure 5 shows a typical titration curve for samples containing carbonyl sulfide. The inflection
point on a carbonyl sulfide titration curve occurs at about -0.1 to +0.1V.
Manual Titration
Automatic titration using the listed equipment is recommended. However, if only manual titration
equipment is available, manual titration can be performed.
Add the silver nitrate solution in increments of 0.2 mL and record the emf after each addition until
the endpoint is approached. Then, reduce the increments to 0.1 mL. The endpoint is found where
emf/mL is a maximum, i.e., where the change in emf per increment of titrant added is the greatest.
If both sulfide and mercaptide are present, 2 inflections will be observed. Make a plot of the titration,
i.e., emf vs. volume of silver nitrate.
Estimate the midpoint of the inflections by inspecting the titration curve, or plot emf/mL and take
the maximum as the endpoint. Record the volumes of silver nitrate used for the titration of the sulfide
and mercaptide respectively. (See Figure 4 for typical titration curves.)
Use the same procedure when the carbonyl sulfide is titrated manually. (See Figure 5 for a typical
titration curve.)

CALCULATIONS
The calculations below use metric units. When calculating values using metered gas volumes of
sample, and the gas meter is calibrated in cubic feet, use the calculations in the APPENDIX. The
APPENDIX also includes calculations for reporting results in grains of sulfur per 100 cubic feet.
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Hydrogen Sulfide
To calculate the concentration of hydrogen sulfide as sulfur, in mass-ppm, from the metered gas
volume of sample used, use Equation 1.
Hydrogen sulfide as sulfur, mass-ppm =

16030 AMY
VCDZ

(1)

where:

A = volume of standard silver nitrate solution used for titrating the sulfide, mL
C = factor for converting the metered gas volume to 15C and 1013 mbar,
calculated from Equation 2:
Correction factor =

288(P PV )
1013(273 + t )

(2)

where:

P = barometric pressure, mbar

PV = vapor pressure of water at temperature t, mbar. At normal room
temperature, 22C, the vapor pressure of water is about 27 mbar.
For a more precise number, or for a different temperature, consult a
technical handbook such as the Handbook of Chemistry and
Physics.
t = meter temperature, C
273 = absolute zero, C, absolute value
288 = 273, previously defined + 15, standard temperature, C
1013 = standard pressure, mbar
D = gas density corrected to 15C and 1013 mbar, g/L, (obtained by ASTM Method
D 1070, Relative Density of Gaseous Fuels, or UOP Method 948, Relative
Density of Gas Mixtures by Calculation from Composition)
M = molarity of the standard silver nitrate solution used for titration, moles/L
V = metered gas volume before correction to 15C and 1013 mbar, L
Y = total volume to which the potassium hydroxide scrubber solution is diluted
before aliquoting, mL. (If the entire scrubber contents are titrated, delete the
terms Y and Z from the equation since they become identical and cancel out.)
Z = volume of the aliquot taken for titration, mL
16030 = factor for converting to mass-ppm sulfur, equal to the product of:

(32.06)(10 6 )
(2)(10 3 )
where:

32.06 =
106 =
2=
103 =

molecular weight of sulfur, g/mole

conversion of g to g
conversion of moles of silver nitrate to moles of sulfur from H2S
conversion of L to mL

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To calculate the concentration of hydrogen sulfide, in mass-ppm, from the measured cylinder
weight difference, use Equation 3.

Hydrogen sulfide as sulfur, mass-ppm =

16030 AMY
GZ

(3)

where:

G = weight of sample taken by cylinder difference, g

A, M, Y, Z = previously defined
16030 = previously defined
Mercaptan Sulfur
To calculate the concentration of mercaptan sulfur, in mass-ppm, from the metered gas volume of
sample used, use Equation 4.

Mercaptan sulfur as sulfur, mass-ppm =

32060BMY
VCDZ

(4)

where:

B = volume of standard alcoholic silver nitrate solution used for titrating the
mercaptide, mL
C, D, M, V, Y, Z = previously defined
32060 = factor for converting to mass-ppm sulfur, equal to the product of:
(32.06)(10 6 )
(10 3 )
where:

32.06 = molecular weight of sulfur, g/mole

106 = conversion of g to g
103 = conversion of L to mL
To calculate the concentration of mercaptan sulfur, in mass-ppm, from the measured cylinder
weight difference, use Equation 5.

Mercaptan sulfur as sulfur, mass-ppm =

32060BMY
GZ

(5)

where:

B, G, M, Y, Z = previously defined
32060 = previously defined
Carbonyl Sulfide
To calculate the concentration of carbonyl sulfide, in mass-ppm, from the metered gas volume of
sample used, use Equation 6.

Carbonyl sulfide as sulfur, mass-ppm =

16030EM
VCD

(6)

where:

E = volume of standard alcoholic silver nitrate solution used for titrating the
carbonyl sulfide, mL
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C, D, M, V = previously defined
16030 = previously defined
To calculate the concentration of carbonyl sulfide, in mass-ppm, from the measured cylinder weight
difference, use Equation 7.

Carbonyl sulfide as sulfur, mass-ppm =

16030EM
G

(7)

where:

E, G, M = previously defined
16030 = previously defined
Report each sulfur type to the nearest 1 ppm as sulfur.

NOTES AND PRECAUTIONS

1. The sample cylinder should be pressure checked with a gauge before scrubbing to ensure that it is
only under LPG vapor pressure, and has not been additionally pressurized with a gas. Typically,
LPG-only pressure is not greater than 1000 kPa. Additional pressure may cause caustic splashes.
If the pressure is greater than 1000 kPa, check the source and history of the sample, and resample
if necessary.
2. The regulating stem of the expansion valve should be cleaned and maintained regularly to ensure
smooth delivery of the LPG into the caustic scrubber to avoid splashes. Cleaning is performed by
rinsing with water, to ensure that it provides a smooth, regular flow without any blockages.
Additional maintenance requires either a rebuild kit, returning to the manufacturer, or
replacement.
3. The use of a face shield is recommended during the scrubbing process in addition to the usual
safety glasses, gloves, and other appropriate personal protection equipment.
4. For refinery sampling, the sample lines should be as short as possible. Purge them with the
sample prior to attaching the scrubber.
5. Use rubber tubing to connect the scrubber to the sample point and to the wet test meter because of
its flexibility. Make the length as short as practical.
6. Analyze the absorber solutions as soon as possible, and protect them from air to minimize
oxidation of the sulfide and mercaptide.
7. Always pass the hydrocarbon gas through the scrubber before passing it through the wet test
meter. This prevents contamination of the meter with hydrogen sulfide.
8. Protect the monoethanolamine solution from exposure to light.
9. The calculations assume that, for practical purposes, the metered gas volume represents the
volume of gas analyzed. The difference represents the volume of hydrogen sulfide in the sample
which normally has no significant effect. For unusual samples which contain hydrogen sulfide in
the percent range, the analyst may refine the calculations to take this into account.
10. Dispose of all used solutions in an environmentally safe manner.

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PRECISION AND BIAS

Precision statements were determined using UOP Method 999, from precision data obtained using a
Brinkmamm Metrohm Model 751GPD Titrino titrator with an automatic sample changer.

Intermediate Precision
A single sample was analyzed four times by each of two analysts over a period of eight days in one
laboratory. The precision data are summarized in Table 2. Two tests performed in one laboratory by
different analysts on different days should not differ by more than the intermediate precision
allowable difference with 95% confidence.
The data in Table 2 are an estimate of intermediate precision. When the test is run routinely, a
control standard and chart should be used to develop a better estimate of the long-term repeatability.

Table 2
Intermediate Precision, mass-ppm Sulfur
Intermediate
Precision
LPG Sample
Hydrogen sulfide
Mercaptan sulfur
Carbonyl sulfide

Mean
Value
2.8
5.2
0.7

WithinLab esd
0.27
0.27
0.05

Allowable
Difference
1.0
1.2
0.2

Reproducibility
There is insufficient data to calculate reproducibility of the test at this time.

Bias
The LPG sample that was used to develop the precision statement was also analyzed for total sulfur
by ASTM Method D 6667. D 6667 measured 8.6 mass-ppm total sulfur, compared to a sum of 8.7
mass-ppm sulfur for this method.

TIME FOR ANALYSIS

Samples Containing Hydrogen Sulfide, Mercaptan, and Carbonyl Sulfide Sulfur
The elapsed time for one analysis is four hours. The labor requirement is four hours. Additional
time is required to initially assemble the apparatus. Samples with very low sulfur levels may require
additional scrubbing time, up to a total of 10 hours.

Samples Containing Mercaptan Sulfur Only and Appreciable

Concentrations of Pentane and Higher Boiling Materials
The elapsed time for one analysis is three hours. The labor requirement is three hours.

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SUGGESTED SUPPLIERS
Acros Organics, Fisher Scientific, 711 Forbes Ave., Pittsburgh, PA 15219-4785 (412-490-8300)
www.fishersci.com
Aldrich Chemical Company, 1000 West Saint Paul Ave., Milwaukee, WI 53233 (414-273-3850)
www.sigma-aldrich.com
Alltech Associates Inc., 2051 Waukegan Rd., Deerfield, IL 60015 (847-948-8600)
www.alltechweb.com
Brinkmann Instruments Co., One Cantiague Rd., Westbury NY 11590 (516-334-7500)
www.brinkmann.com
Fisher Scientific Co., 711 Forbes Ave., Pittsburgh, PA 15219-4785 (412-490-8300)
www.fishersci.com
Matheson Tri-Gas, 166 Keystone Drive, Montgomeryville, PA 18936 (215-641-2700)
www.mathesontrigas.com
Meters & Controls, 505 W. Wrightwood Ave., Elmhurst, IL 60126 (630-279-3800)
www.americanmeter.com
Reliance Glass, 2220 Gateway Road, Bensenville, IL 60106 (630-766-1816) www.lab-glass.com
Runco Office Supply, 1108 Lee St., Des Plaines, IL 60016 (847-297-7740) www.runcoonline.com
Swagelok, 1540 N. Old Rand Road, Wauconda, IL 60084-0847 (847-526-6900)
www.swagelok.com

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APPENDIX
The appendix is written as a convenience for users who measure the sample quantity scrubbed from
the metered gas volume of sample used, and whose equipment for SCRUBBING OF GASES is
calibrated in English units (cu ft, F). Also included are calculations for reporting results in grains of
sulfur per 100 cubic feet.

CALCULATIONS
Hydrogen Sulfide
To calculate the concentration of hydrogen sulfide, in mass-ppm, from the metered gas volume of
sample used, use Equation A1.

Hydrogen sulfide as sulfur, mass-ppm =

566 AMY
VCDZ

( A1)

where:

A = volume of standard silver nitrate solution used for titrating the sulfide, mL
C = factor for converting the metered gas volume to 60F and 760 mm Hg. This can
be conveniently ascertained from the Gas Volume Correction Chart, Figures
A1 and A2. Alternatively, it can be calculated from Equation A2:
Correction factor =

520 (P PV )
760 (460 + t)

( A 2)

where:

P = barometric pressure, mm Hg
PV = vapor pressure of water at temperature t, mm Hg. At normal
room temperature, 72F, the vapor pressure of water is about 20
mm Hg. For a more precise number, or for a different
temperature, consult a technical handbook.
t = meter temperature, F
460 = absolute zero, F, absolute value
520 = 460, previously defined + 60, standard temperature, F
760 = standard pressure, mm Hg
D = gas density corrected to 60F and 760 mm Hg, g/L, (obtained by ASTM
Method D 1070, Relative Density of Gaseous Fuels, or UOP Method 948,
Relative Density of Gas Mixtures by Calculation from Composition)
M = molarity of the standard silver nitrate solution used
V = metered gas volume before correction to 60F and 760 mm Hg, cu ft
Y = total volume to which the potassium hydroxide scrubber solution is diluted
before aliquoting, mL. (If the entire scrubber contents are titrated, delete the
terms Y and Z from the equation since they become identical and cancel out.)
Z = volume of the aliquot taken for titration, mL
566 = factor for converting to mass-ppm sulfur, equal to the product of:
(32.06)(10 6 )
(2)(28.316)(10 3 )
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where:

32.06 =
106 =
2=
28.316 =
103 =

molecular weight of sulfur, g/mole

conversion of g to g
conversion of moles of silver nitrate to moles of sulfur from H2S
conversion of cu ft to L of gas, L/cu ft
conversion of L to mL

To calculate the concentration of hydrogen sulfide in grains per 100 cu ft at standard temperature
and pressure (STP, 60F, 760 mm Hg), use Equation A3.

Hydrogen sulfide as sulfur, grains/100 cu ft at STP =

24.73 AMY
0.000418 AMY + VCZ

( A 3)

where:

A, C, M, V, Y, Z = previously defined
24.73 = factor for converting to grains of sulfur per 100 cu ft of gas at STP, equal to the
product of:
(32.06)(15.43)(10 2 )
(2)(10 3 )
where:

32.06 =
15.43 =
102 =
2=
103 =

molecular weight of sulfur, g/mole

conversion from grams of sulfur to grains of sulfur, grains/g
conversion from per cu ft of gas to per 100 cu ft of gas
conversion of moles of silver nitrate to moles of sulfur from H2S
conversion of L to mL

0.000418 = factor for correcting the metered gas volume for the volume of H2S adsorbed
by the scrubbers, equal to the product of:
(23.67)
(28.316)(2)(10 3 )
where:

23.67 =
28.316 =
2=
103 =

conversion from moles to liters of gas at STP, L/mole

conversion of cu ft to L of gas, L/cu ft
conversion of moles of silver nitrate to moles of sulfur from H2S
conversion of L to mL

For gases containing less than 200 grains of hydrogen sulfide per 100 cu ft, the term 0.000418
AMY in the denominator, which represents the cubic feet of hydrogen sulfide in the sample, is
negligible and may be eliminated from the formula. This simplifies the expression to Equation A4:

Hydrogen sulfide as sulfur, grains/100 cu ft at STP =

24.73 AMY
VCZ

( A 4)

where:

A, C, M, V, Y, Z = previously defined
24.73 = factor for converting to grains of sulfur per 100 cu ft of gas at STP, previously
defined
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Mercaptan Sulfur
To calculate the concentration of mercaptan sulfur, in mass-ppm, from the metered gas volume of
sample used, use Equation A5.

Mercaptan sulfur as sulfur, mass-ppm =

1132BMY
VCDZ

( A5)

where:

B = volume of standard alcoholic silver nitrate solution used for titrating the
mercaptide, mL
C, D, M, V, Y, Z = previously defined
1132 = factor for converting to mass-ppm sulfur, equal to the product of:
(32.06)(10 6 )
(28.316)(10 3 )
where:

32.06 =
106 =
28.316 =
103 =

molecular weight of sulfur, g/mole

conversion of g to g
conversion of cu ft to L of gas, L/cu ft
conversion of L to mL

To calculate the concentration of mercaptan sulfur in grains per 100 cu ft at STP, use Equation A6.

Mercaptan sulfur as sulfur, grains/100 cu ft at STP =

49.47BMY
VCZ

( A 6)

where:

B, C, M, V, Y, Z = previously defined
49.47 = factor for converting to grains of sulfur per 100 cu ft of gas at STP, equal to the
product of:
(32.06)(15.43)(10 2 )
(10 3 )
where:

32.06 =
15.43 =
102 =
103 =

molecular weight of sulfur, g/mole

conversion from grams of sulfur to grains of sulfur, grains/g
conversion from per cu ft of gas to per 100 cu ft of gas
conversion of L to mL

Carbonyl Sulfide
To calculate the concentration of carbonyl sulfide, in mass-ppm, from the metered gas volume of
sample used, use Equation A7.

Carbonyl sulfide as sulfur, mass-ppm =

where:
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566EM
VCD

( A 7)

23 of 25

E = volume of standard alcoholic silver nitrate solution used for titrating the
carbonyl sulfide, mL
C, D, M, V = previously defined
566 = factor for converting to mass-ppm sulfur, equal to the product of:
(32.06)(10 6 )
(2)(28.316)(10 3 )
where:

32.06 = molecular weight of sulfur, g/mole

106 = conversion of g to g
2 = conversion of moles of silver nitrate to moles of sulfur from
COS
28.316 = conversion of cu ft to L of gas, L/cu ft
103 = conversion of L to mL
Report all sulfur types to the nearest 1 ppm as sulfur, or to the nearest 0.1 grains per 100 cu ft at STP.

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Figure A1

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Figure A2

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