TOTAL CHLORIDE IN ALUMINA

AND SILICA-ALUMINA CATALYSTS

BY POTENTIOMETRIC TITRATION
UOP Method 291-02

SCOPE

This method is for determining the total inorganic chloride content of fresh or spent alumina and
silica-alumina catalysts or catalyst supports. The range of quantitation is 0.01 to 10 mass-%.

OUTLINE OF METHOD

The as-received sample is weighed into a beaker and digested with hot dilute sulfuric acid.
Promoter metals, if present, are reduced with magnesium. Chloride is determined potentiometrically
by titration with a silver nitrate solution using a silver-silver chloride indicating electrode system.
An alternative digestion procedure, using a microwave oven, is described in the APPENDIX.

APPARATUS

References to catalog numbers and suppliers are included as a convenience to the method user.
Other suppliers may be used.

Balance, readabi1ity 0.1-mg

Beaker, electrolytic, extra high form, without spout, 250-mL, Reliance Glass Works, Cat. No. G-
9906-002

Bottle, washing 500-mL, polyethylene, Fisher Scientific, Cat. No. 03-409-10E

Condenser, acorn type (see Figure), Reliance Glass Works, Cat. No. G-9906-002C

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 1963, 1965, 1976, 1986, 1989, 2002 UOP LLC

ALL RIGHTS RESERVED
Marks of other proprietors may appear incidentally in this method for purposes such as product or service identification, but no
claim is made to any other proprietors mark used.
UOP Methods are available through ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA
194428-2959, United States. The 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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Cylinders, graduated, standard Class B borosilicate glass, 100- and 250-mL, Fisher Scientific, Cat.
Nos. 08-08-550E and 550F, respectively

Electrode, combination glass/silver TitrodeTM, MetrohmTM 6.0430.100, Brinkmann Instruments,

Cat. No. 20 94 850-7. The electrode should be dedicated to chloride analysis.

Hot plate, electric

Oven, drying

Scotchbrite cleaning pads, or equivalent, local supply

Stir bar, magnetic, 38-mm length, Fisher Scientific, Cat. No. 14-511-64

Titrator, potentiometric, recording, 2000-mV range, 1-mV resolution with dispenser having a
volume readout of 0.00-99.99 mL and 0.01-mL resolution, Metrohm 751GPD or 736GP
TitrinoTM system with optional 730 sample changer, and two 20-mL burets, one for each titrant,
Brinkmann Instruments

Tongs, TefzelTM, 250-mm long, Cole-Parmer Instrument, Cat. No. U-06442-00

Watch glass, borosilicate glass, 65-mm diameter, Cole-Parmer, Cat. No. U-34507-01

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Figure
Condenser-Beaker Assembly

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REAGENTS AND MATERIALS

References to catalog numbers and suppliers are included as a convenience to the method user.
Other suppliers may be used.

Boiling chips, silicon carbide, Thomas Scientific, Cat. No. 1590-D33

Congo red test strips, Fisher Scientific, Cat. No. 14-861

Magnesium, metal turnings, Fisher Scientific, Cat. No. M11

Potassium chloride, primary standard, oven dried at 105C for 2.5 hours, Fisher Scientific, Cat. No.
P217-500

Potassium chloride solution, saturated, Fisher Scientific, Cat. No. SP138-500

Silver nitrate, 0.10-M standard aqueous solution, Fisher Scientific, Cat. No. SS72-500. If the
0.01-M silver nitrate solution is purchased with a Certificate of Analysis, the Silver Nitrate
Standardization step under PROCEDURE may be eliminated.

Silver nitrate, 0.01-M standard aqueous solution. Dilute one part of the 0.10-M aqueous solution
with 9 parts of water.

Sulfuric acid, concentrated, Fisher Scientific, Cat. No. A300-500

Sulfuric acid, approximately 3.5-M. Dilute 200 mL of concentrated acid to one liter with water.
The diluted acid should never be stronger than 4-M. Add the concentrated acid cautiously to the
cold water while stirring. The 3.5-M sulfuric acid may also be purchased, Fisher Scientific, Cat.
No. SX-350.

Sulfuric acid, 1:1 dilution. Mix equal volumes of concentrated sulfuric acid and water. Add the
concentrated acid cautiously to the cold water while stirring.

Water, distilled

Wipers, Kimwipes Ex-L, Fisher Scientific, Cat. No. 06-666A

PROCEDURE
SilverSilver Chloride Electrode Preparation and Reconditioning
Proper electrode preparation is essential to obtain reproducible and noise-free titration curves
having good endpoints. The electrode must be reconditioned prior to running samples. An electrode
should be dedicated to chloride analysis. Prepare and recondition the silver-silver chloride electrode
as follows:

1. Clean the silver surface with a Scotchbrite pad. Rinse with water and dry.

2. Weigh approximately 0.1 g of potassium chloride and place in a beaker. Using a graduated
cylinder, add 20 mL of 3.5-M sulfuric acid and 80 mL of water to the beaker. Immerse the
electrode; and titrate to the endpoint with 0.10-M silver nitrate.

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3. Remove the electrode from the solution and rinse with water.

4. Wipe the excess silver chloride from the electrode with a wiper.

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

The freshly coated silver-silver chloride electrode may be stored in water or carefully dried using
wipers and stored for future use. It is necessary to repeat the electrode preparation when the AgCl
begins to peel from the surface.

Silver Nitrate Standardization

Standardize the 0.1-M silver nitrate solution with potassium chloride as follows:

1. Weigh between 0.09 and 0.10 g of dried potassium chloride to the nearest 0.1 mg into a clean,
dry 250-mL electrolytic beaker.

2. Using a graduated cylinder, add 100 mL of water. Add a stirring bar. Acidify to congo red
with 1:1 sulfuric acid.

3. While stirring at a moderate rate, titrate with 0.1-M silver nitrate solution.

Calculate the molarity of the silver nitrate to 3 significant figures using Eq. 1:

AgNO3, M = A (1)
0.07455B
where:
A = mass of potassium chloride weighed into beaker, g
B = volume of silver nitrate solution used in titration, mL
0.07455 = molecular weight of the potassium chloride multiplied by 0.001, the factor to
convert milliliters to liters

Sample Analysis

Sample digestion/reduction can be accomplished by conventional heating, as follows, or by

microwave heating (see NOTE and APPENDIX).

Samples of fresh or spent catalyst that contain promoter (usually noble) metals must be reduced
as described under Reduction, after Digestion, before Titration. Catalyst bases do not require
reduction.

Digestion

1. Weigh approximately 2 g of the as-received catalyst or catalyst base to the nearest 0.1 mg into
a 250-mL electrolytic beaker. When results are to be reported on a volatile-free basis, weigh
out a separate portion of the sample for the determination of LOI, as directed in UOP Method
275, at the same time the sample is weighed for chloride.
2. Using a graduated cylinder, add 75 mL of 3.5-M sulfuric acid to the beaker containing the
sample for chloride determination. Add several boiling chips.

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3. Place the beaker on a cool hot plate, located in a hood or well-ventilated area, and place an
acorn condenser in the top of the beaker.

4. Start cold tap water running through the condenser and turn on the hot plate. Heat the sample
to just below the boiling point (do not allow to boil) until the catalyst is completely digested, or
for a maximum of 6 hours. Fresh alumina catalyst or base will usually require about 2 hours
for complete digestion, while used alumina catalyst or any silica-alumina catalyst may not
completely dissolve, even after 6 hours.

5. Remove the beaker from the hot plate with the acorn condenser in place and allow it to cool so
that it can be handled comfortably.

6. Lift off the acorn condenser and rinse it with water, catching the rinsings in the beaker. Cover
with a watch glass.
For some installations, especially those with multiple hot plates and acorn condensers, the water line
connections to the acorn condenser may not permit removal of the beaker from the hot plate with the
condenser in place. In this case, it is permissible to quickly lift the condenser, rinse it, cover the beaker
with a watch glass, and remove the beaker from the hot plate.

7. Reduce the promoter metals, if present, as described in Reduction.

8. Continue the sample analysis as described under Titration.

Reduction

1. Add a small stirring bar to each beaker and start the magnetic stirrer.

2. Add approximately 0.6 g of magnesium turnings and cover with the watch glass

3. When the magnesium has completely dissolved, rinse the watch glass catching the rinsings in
the beaker.

4. Continue the sample analysis as described under Titration.

Titration

1. Condition the electrodes prior to running samples as described in SilverSilver Chloride

Electrode Preparation and Reconditioning.

2. Prior to titration, add sufficient water to ensure complete electrode immersion, typically to about
100 mL total volume.

3. Titrate the sample with 0.10-M silver nitrate at a titration rate of about 2.5 mL/min using a
moderately fast stirring rate (no vortex or splashing). As the endpoint is approached, reduce the
titration rate to approximately 0.1 mL/min. For chloride levels below 0.05 mass-%, titrate with
0.01-M silver nitrate.

The endpoint of the titration corresponds to that volume of titrant at which the rate of change of
potential, EMF/ mL, reaches a maximum. If a recording titrator is used, a plot is automatically
generated. Alternatively, EMF vs. milliliters of titrant added can be manually plotted and the
endpoint determined from the inflection point of the titration curve.

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Obtain a reagent blank (3.5-M sulfuric acid) each time that fresh reagent is used. Follow the same
titration procedure used in the sample analysis. If the titration of the blank requires more than 0.10
mL of 0.10-M silver nitrate, the reagents are not acceptable.

CALCULATION

Calculate the chloride content of the sample to the nearest 0.01 % as follows:

A) As-received basis:
3.545(C D)M
Chloride, mass-% = (2)
W
B) Volatile-free basis:
3.545(C D)M (3)
Chloride, mass-% = 100 V
W( )
100
where:
C= volume of silver nitrate to reach the chloride endpoint, mL
D= volume of silver nitrate required for reagent blank, mL
M= molarity of silver nitrate
V= loss on ignition determined by UOP Method 275, mass-%
W= sample mass, g
3.545 = 0.03545 times 100, factor combining the millimolar weight of chlorine and the
factor to convert mass fraction to mass-%

NOTE
An alternative digestion procedure using a microwave heating technique is described in the
APPENDIX. Data from a comparative study has shown that conventional or microwave heating
produce equivalent results. If microwave heating is used, the condenser and hot plate under
APPARATUS are not required.

PRECISION
The precision statements were determined using UOP Method 999.

ASTM and UOP Repeatability

A nested design was carried out for determining chloride in oxidized and reduced catalysts with two
analysts in each of five laboratories. Each analyst carried out tests on two separate days, performing
two tests each day. The total number of tests performed was 120. The precision data are summarized
in Table 1. Two tests performed by the same analyst on the same day should not differ by more than
the ASTM allowable difference with 95% confidence. Two tests performed in one laboratory by
different analysts on different days should not differ by more than the UOP allowable difference with
95% confidence.

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The data in Table 1 are a short-term estimate of repeatability. 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 1
ASTM and UOP Repeatability and Reproducibility, Mass-%
ASTM Repeatability UOP Repeatability Reproducibility
Within-
Mean Lab and
Catalyst Chloride Within- Allowable Within- Allowable Between- Allowable
Sample Conc. Day esd Difference Lab esd Difference Lab esd Difference
Oxidized 1.18 0.012 0.04 0.014 0.04 0.017 0.05
Oxidized 1.10 0.016 0.05 0.016 0.05 0.020 0.06
Reduced 1.05 0.015 0.05 0.014 0.04 0.023 0.08

Reproducibility

A nested design was carried out for determining chloride in oxidized and reduced catalysts with two
analysts in five laboratories. Each analyst carried out tests on two separate days, performing two tests
each day. The total number of tests performed was 120. The precision data are summarized in Table
1. Two tests performed by different analysts in different laboratories on different days should not
differ by more than the allowable difference shown in Table 1 with 95% confidence.

TIME FOR ANALYSIS

The total elapsed time for an analysis is 7 hours. The labor requirement per analysis is 1.6 hours
when done singly or 0.8 hour when done in groups of 6 or more.

REFERENCE

UOP Method 275, www.astm.org

SUGGESTED SUPPLIERS

Aldrich Chemical Co., Inc., 1000 West Saint Paul Avenue, Milwaukee, WI 53233 (414-273-3850)
www.sigma-aldrich.com
Brinkmann Instruments Co., One Cantiague Rd., Westbury, NY 11590 (516-334-7500)
www.brinkmann.com
Cole-Parmer, 625 East Bunker Court, Vernon Hills, IL 60061-1844 (847-549-7600)
www.coleparmer.com
Fisher Scientific Co., 711 Forbes Ave., Pittsburgh, PA 15219-4785 (412-490-8300)
www.fishersci.com
Reliance Glass Works, 220 Gateway Road, Bensenville, IL 60106 (630-766-1816)
www.relianceglass.com
Thomas Scientific, P.O. Box 99, Swedesboro, NJ 08085-0090 (856-467-2000)
www.thomassci.com

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APPENDIX

Microwave Digestion of Catalyst

SCOPE

This appendix describes an alternative catalyst digestion procedure using a microwave heating
technique. Data from a comparative study has shown that conventional or microwave heating
produce equivalent results. If microwave heating is used, the condenser and hot plate under
APPARATUS in the body of the method are not required.

OUTLINE OF METHOD

The as-received sample is weighed into a TeflonTM vessel and dilute sulfuric acid is added. The
vessel is placed in a specially configured microwave oven and heated for several minutes. The
sample is then titrated as described in the body of the method.

APPARATUS
References to catalog numbers and suppliers are included as a convenience to the method user.
Other suppliers may be used.

The following apparatus is an addition or substitution to that listed in the body of the method:

Capping station, CEM, Cat. No. 920030

Carousel (turntable), 12-position. Teflon, CEM Cat. No. 221049

Cylinder, graduated, 50-mL, Fisher Scientific, Cat. No. 08-552D

Microwave, 600 watt, CEM, Model MARS 5

Tube, transfer, Teflon, CEM, Cat. No. 324360

Vessel, 120-mL, Teflon, with cap and pressure seal, CEM, Cat, No. 221000

REAGENTS AND MATERIALS

References to catalog numbers and suppliers are included as a convenience to the method user.
Other suppliers may be used.

The following reagents and materials are an addition or substitution to those listed in the body
of the method:

Sulfuric acid, 20 vol/vol-%, To prepare, slowly add 200 mL of concentrated sulfuric acid to
800 mL of water and mix thoroughly.

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PROCEDURE

1. Weigh approximately 2 g of the as-received catalyst or catalyst support to the nearest 0.1 mg into
a 120-mL Teflon vessel. When results are to be reported on a volatile-free basis, weigh out a
separate portion of the sample for the determination of LOI as directed in UOP Method 275, at
the same time the sample is weighed for chloride.

2. Using a graduated cylinder, add 30 mL of 20% sulfuric acid to the Teflon vessel.

3. Place a pressure seal on the vessel with the flat side down. Screw the cap onto the vessel until
finger tight. Place the vessel in the capping station and press the toggle switch to tighten the
cap. Use of the capping station is required to ensure proper torque and sealing of the vent seal.
Remove the capped vessel from the capping station and place it on the carousel.

4. Insert a Teflon transfer tube into the fitting on the top of the cap and hand tighten the
connection. Insert the other end of the tube into the center catch vessel. The transfer tube is a
safety precaution to vent excessive pressure buildup in the vessel. If any liquid is vented from
a sample during the digestion, as indicated by the presence of droplets in the transfer tube, the
sample must be rerun.

5. Repeat the above procedure with additional samples until the carousel contains either 6 sample
vessels (distributed around the carousel) or 12 sample vessels. If it is necessary to run a fewer
number of samples, fill the remaining vessels with blanks containing 30 mL of sulfuric acid.
Place the carousel in the microwave. Set the switches for power and turntable to the "on"
position and fan to "full power. Set the power and time program for the appropriate number of
samples as shown in Table A1. Include at the end of the timing sequence a 20-minute period at
0% power for cooling.

Table A1
Number of Samples Time, Minutes Power Setting, Watts
12 17 600
6 8 600

6. Remove the carousel from the microwave. Loosen the fittings on the transfer tubes and remove
them from the vessels. Place a vessel in the capping station and press the toggle switch to loosen
the cap. Remove the vessel from the station and complete removal of the cap by hand.

7. Carefully rinse the seal and the inside of the cap with water, catching the rinsings in the vessel.
If any aluminum sulfate crystals form in the sample solution, warm slightly in the microwave.

8. Quantitatively transfer the solution with water to a 250-mL electrolytic beaker.

9. Add a small stirring bar to each beaker and start the magnetic stirrer. Add approximately 0.6 g
of magnesium turnings and cover with a watch glass. When the magnesium has completely
dissolved, rinse the watch glass catching the rinsings in the beaker.

10. Titrate the sample as described in the body of the method.

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PRECISION

The precision statements were determined using UOP Method 999.

ASTM and UOP Repeatability

A nested design was carried out to compare conventional and microwave digestion with two analysts
in one laboratory. Each analyst carried out tests on two separate days, performing two tests each day.
The total number of tests performed was 48. The precision data are summarized in Table A2. Two
tests performed by the same analyst on the same day should not differ by more than the ASTM
allowable difference with 95% confidence. Two tests performed in one laboratory by different
analysts on different days should not differ by more than the UOP allowable difference with 95%
confidence.

Reproducibility

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

Table A2
ASTM and UOP Repeatability, Mass-%
ASTM Repeatability UOP Repeatability
Mean
Catalyst Chloride Within- Allowable Within- Allowable
Sample Digestion Conc. Day esd Difference Lab esd Difference
Oxidized Conventional 1.19 0.017 0.05 0.019 0.06
Microwave 1.19 0.013 0.04 0.012 0.04
Oxidized Conventional 1.08 0.033 0.10 0.026 0.08
Microwave 1.07 0.025 0.07 0.019 0.06
Reduced Conventional 1.11 0.029 0.08 0.022 0.06
Microwave 1.10 0 0 0.007 0.02

TIME FOR ANALYSIS

The elapsed time for an analysis is one hour. The labor requirement is 0.8 hour.

SUGGESTED SUPPLIERS

CEM Corporation, PO Box 200, Matthews, NC 28106-0200 (704-821-7015) www.cem.com

Fisher Scientific Co., 711 Forbes Ave., Pittsburgh, PA 15219-4785 (412-490-8300)
www.fishersci.com

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