Chloride DOC316.53.

01306

Silver Nitrate Method Method 10246

100 to 200,000 mg/L as Cl– Digital Titrator
Scope and application: For oil and gas field waters.

Test preparation

Before starting
As an alternative to stirring by hand, use the TitraStir Titration Stand to hold the Digital Titrator and stir the sample.
Review the Safety Data Sheets (MSDS/SDS) for the chemicals that are used. Use the recommended personal protective
equipment.
Dispose of reacted solutions according to local, state and federal regulations. Refer to the Safety Data Sheets for disposal
information for unused reagents. Refer to the environmental, health and safety staff for your facility and/or local regulatory
agencies for further disposal information.

Items to collect
Description Quantity

Chloride 2 Indicator Powder Pillows 1

Silver Nitrate Titration Cartridge, 1.128 N 1
Digital Titrator 1
Delivery tube for Digital Titrator 1
Graduated cylinder (size varies with selected sample volume), or TenSette pipet with tips 1
Erlenmeyer flask, 250-mL 1
Water, deionized varies

Refer to Consumables and replacement items on page 5 for order information.

Sample collection
• Collect samples in clean glass or plastic bottles.
• The sample can be kept for a maximum of 7 days before analysis.

Determine the sample volume

Use the steps that follow to make an estimate of the sample volume to use in the test
procedure.

1. Add approximately 75–100 mL of deionized water to a clean titration flask.

2. Use a TenSette pipet to add 0.1 mL of the sample to the titration flask. Swirl to mix.
3. Add the contents of one Chloride 2 Indicator Powder Pillow to the flask. Swirl to mix.
The sample color becomes yellow.
4. Titrate the solution quickly with the Silver Nitrate Titration Cartridge until the color
changes from yellow to red-brown. Refer to Technique tips on page 3. Record the
number of digits on the counter.
5. Find the sample volume to use in the test procedure from Table 1.
6. Rinse the flask fully with deionized water.

1
 Table 1 Determine the sample volume
Number of digits Sample volume (mL)
250 0.1
125 0.2
50 0.5
25 1.0
10 2.0
5 5.0
2 20
1 50

Test procedure

1. Select a sample volume 2. Insert a clean delivery 3. Hold the Digital Titrator 4. Use a graduated cylinder
and titration cartridge from tube into the Silver Nitrate vertically with the cartridge or TenSette pipet to
Table 2 on page 3. Titration Cartridge. Attach tip up. Turn the delivery measure the sample volume
Refer to Determine the the cartridge to the Digital knob to eject air and a few from Table 2 on page 3.
sample volume on page 1. Titrator. drops of titrant. Reset the
Keep the silver nitrate counter to zero and clean
cartridge in a dark area the tip.
when not in use.

5. Pour the sample into a 6. If the sample volume is 7. Add the contents of one 8. Swirl to mix.
clean, 250-mL Erlenmeyer less than 100 mL, dilute to Chloride 2 Indicator Powder A small amount of
flask. approximately 100 mL with Pillow. undissolved powder will not
deionized water. have an effect on the
results.

2 Chloride, Digital Titrator, Oil and Gas (200,000 mg/L)

9. Put the delivery tube 10. Use the multiplier in
point fully into the solution Table 2 on page 3 to
and swirl the flask. Turn the calculate the concentration.
knob on the Digital Titrator Digits used × digit multiplier
to add titrant to the solution. = mg/L Cl–
Continue to swirl the flask
and add titrant until the color
changes from yellow to red-
brown. Refer to Technique
tips on page 3. Record
the number of digits on the
counter.

Sample volumes and digit multipliers

Select a range in Table 2, then read across to find the applicable information for this test.
Use the digit multiplier to calculate the concentration in the test procedure.
Note: Refer to Determine the sample volume on page 1 to find a sample volume for this test.
Example: A 50-mL sample was titrated and the counter showed 250 digits at the
endpoint. The concentration is: 250 digits x 1 = 250 mg/L Cl–.
Table 2 Sample volumes and digit multipliers
Range (mg/L as Cl–) Sample volume (mL) Digit multiplier
100–400 50 1
250–1000 20 2.5
1000–4000 5 10
2500–10,000 2 25
5000–20,000 1 50
10,000–40,000 0.5 100
25,000–100,000 0.2 250
50,000–200,000 0.1 500

Technique tips
• As an alternative to the deionized water, use demineralized water or other sources of
chloride-free water.
• Use the TitraStir Titration Stand to reproducibly stir the sample at a steady rate.
• If the precipitate is red or orange but the solution is yellow, the test result will be low.
Do the test again and increase the stir rate during the titration. Complete the steps
that follow to prevent the red or orange precipitate formation:

Chloride, Digital Titrator, Oil and Gas (200,000 mg/L) 3

 1. Do not add one Chloride 2 Indicator Powder Pillow in step 7 of the test procedure
and go directly to step 8.
2. Titrate a fresh sample with the Silver Nitrate Titration Cartridge to approximately
50–75% of the expected endpoint. The solution will have a milky-white
precipitate.
3. Add one Chloride 2 Indicator Powder Pillow and swirl to dissolve. The solution
becomes yellow. Continue to titrate with the Silver Nitrate Titration Cartridge to
the red-brown endpoint.
If the sample becomes red-brown after the addition of one Chloride 2 Indicator
Powder Pillow, too much titrant was added. Repeat the procedure with less
titrant.

Conversions
To change the units or chemical form of the test result, multiply the test result by the
factor in Table 3.
Table 3 Conversions
mg/L chloride (Cl–) to... multiply by... Example
mg/L sodium chloride (NaCl) 1.65 1000 mg/L chloride x 1.65 = 1650 mg/L NaCl
meq/L chloride (Cl–) 0.02821 1000 mg/L chloride x 0.02821 = 28.21 meq/L Cl–

Interferences
Table 4 shows the substances that can interfere with this test.
Table 4 Interferences
Interfering substance Interference level
Bromide Interferes directly and is included in the test result.
Cyanide Interferes directly and is included in the test result.
Iodide Interferes directly and is included in the test result.
Iron Concentrations that are more than 10 mg/L prevent the color change at the endpoint.
Orthophosphate Concentrations that are more than 25 mg/L will form a precipitate with the silver from the titrant.
Highly buffered samples Can prevent the correct pH adjustment of the sample by the reagents. Sample pre-treatment may
or extreme sample pH be necessary. Neutralize strongly alkaline or acidic samples to a pH of 2 to 7 with 5.25 N sulfuric
acid or 5.0 N sodium hydroxide. If a pH meter is used in the pH adjustment, use a separate
sample to find the correct amount of acid or base to use. Then add the same amount of acid or
base to the sample to be tested. pH electrodes will contaminate the sample.
Sulfide Complete the steps that follow to remove sulfide interference:

1. Add the contents of one Sulfide Inhibitor Reagent Powder Pillow to approximately 125 mL of
sample.
2. Mix for 1 minute.
3. Pour the solution through folded filter paper.
4. Use the filtered sample in the chloride test procedure.

Sulfite Concentrations that are more than 10 mg/L interfere with this method. To eliminate sulfite
interference, add 3 drops of Hydrogen Peroxide, 30%, to the sample before the test is started.

Accuracy check
Standard additions method (sample spike)
Use the standard additions method to validate the test procedure, reagents, apparatus,
technique and to find if there is an interference in the sample.
Items to collect:
• Chloride Voluette Ampule Standard Solution, 12,500-mg/L Cl–

4 Chloride, Digital Titrator, Oil and Gas (200,000 mg/L)

 • Ampule Breaker
• Pipet, TenSette, 0.1–1.0 mL and pipet tips

1. Use the test procedure to measure the concentration of the sample.

2. Use a TenSette pipet to add 0.1 mL of the standard solution to the titrated sample.
3. Titrate the spiked sample to the endpoint. Record the number of digits on the counter.
4. Add one more 0.1-mL addition of the standard solution to the titrated sample.
5. Titrate the spiked sample to the endpoint. Record the number of digits on the counter.
6. Add one more 0.1-mL addition of the standard solution to the titrated sample.
7. Titrate the spiked sample to the endpoint. Record the number of digits on the counter.
8. Compare the actual result to the correct result. The correct result for this titration is 25
digits of the Silver Nitrate Titration Cartridge for each 0.1 mL addition of the standard
solution. If much more or less titrant was used, there can be a problem with user
technique, reagents, apparatus or an interference.

Standard solution method

Use the standard solution method to validate the test procedure, reagents, apparatus and
technique.
Items to collect:
• Chloride Voluette Ampule Standard Solution, 12,500-mg/L Cl–
• Ampule Breaker
• Pipet, TenSette, 0.1–1.0 mL and pipet tips

1. Use a TenSette pipet to add 1.0 mL of the standard solution to a 250-mL Erlenmeyer
flask.
2. Dilute to approximately 100 mL with deionized water.
3. Add one Chloride 2 Indicator Powder Pillow. Swirl to mix.
4. Titrate the prepared standard solution until the color changes from yellow to red-
brown. Refer to Technique tips on page 3. The correct number of digits for this
titration is 250 (± 25) digits.
5. Compare the actual number of digits that were used in the titration to the correct
number of digits. If much more or less titrant was used, there can be a problem with
user technique, reagents or apparatus.

Summary of Method
Silver ions in the titrant react with chloride in the sample to form a silver chloride
precipitate. After all of the chloride is in the form of silver chloride, the silver ions react
with chromate (from the Chloride 2 Indicator Powder Pillow) to form a silver chromate
precipitate. The silver chromate precipitate has an orange or a red-brown color, which
shows the endpoint of the titration.
Consumables and replacement items
Required reagents

Description Quantity/Test Unit Item no.

Chloride Reagent Set (approximately 100 tests) — each 2288000

Chloride 2 Indicator Powder Pillows (2x) 1 50/pkg 105766
Silver Nitrate Titration Cartridge, 1.128 N varies each 1439701
Water, deionized varies 4L 27256

Chloride, Digital Titrator, Oil and Gas (200,000 mg/L) 5

Required apparatus

Description Quantity/test Unit Item no.

Graduated cylinders—select one or more based on the sample volume:

Cylinder, graduated, 5-mL 1 each 50837
Cylinder, graduated, 10-mL 1 each 50838
Cylinder, graduated, 25-mL 1 each 50840
Cylinder, graduated, 50-mL 1 each 50841
Cylinder, graduated, 100-mL 1 each 50842
Digital Titrator 1 each 1690001
Delivery tube for Digital Titrator, J-hook tip 1 5/pkg 1720500
Flask, Erlenmeyer, 250-mL 1 each 50546
®
Pipet, TenSette , 0.1–1.0 mL 1 each 1970001
®
Pipet tips, for TenSette Pipet, 0.1–1.0 mL 1 50/pkg 2185696

Recommended standards

Description Unit Item no.

Chloride Standard Solution, 12,500 mg/L as Cl-, 10-mL Voluette ampules 16/pkg 1425010

Optional reagents and apparatus

Description Unit Item no.

®
Ampule Breaker, 10-mL Voluette Ampules each 2196800
Filter paper, folded, 3–5-micron, 12.5-cm 100/pkg 69257
Funnel, poly, 65-mm each 108367
Hydrogen Peroxide Solution, 30%, ACS 473 mL 14411
Sodium Hydroxide Standard Solution, 5.0 N 100 mL MDB 245032
Stir bar, octagonal each 2095352
Sulfide Inhibitor Reagent Powder Pillows 100/pkg 241899
Sulfuric Acid Standard Solution, 5.25 N 100 mL 244932
TitraStir Titration Stand, 115 VAC each 1940000
TitraStir Titration Stand, 230 VAC each 1940010
Delivery tube for Digital Titrator, 90-degree bend for use with TitraStir Titration Stand 5/pkg 4157800

FOR TECHNICAL ASSISTANCE, PRICE INFORMATION AND ORDERING: HACH COMPANY

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© Hach Company/Hach Lange GmbH, 2011, 2014. All rights reserved. 12/2014, Edition 2