Sulfite DOC316.53.

01162

Iodate-Iodide Method1 Method 8071

0–500 mg/L as SO32– (or 0 to more than 500 mg/L) Buret Titration
Scope and application: For boiler water.
1 Adapted from Standard Methods for the Examination of Water and Wastewater.

Test preparation

Before starting
Samples must be analyzed immediately after collection and cannot be preserved for later analysis.
Let the sample temperature decrease to 50 °C (122 °F) or less before analysis.
Sulfite reacts quickly with oxygen in the air. Shaking or swirling the sample causes low results. Prevent agitation of the
sample during the procedure.
As an alternative to the Dissolved Oxygen 3 Reagent Powder Pillow, use 0.5 mL of 19.2 N Sulfuric Acid Standard Solution.
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

Dissolved Oxygen 3 Reagent Powder Pillow 1

Potassium Iodide-Iodate Standard Solution, 0.0125 N varies
Starch Indicator Solution 1 mL
Buret, Class A, 10 mL 1
Graduated cylinder (use a size that is applicable to the selected sample volume), or TenSette
1
pipet with tips
Erlenmeyer flask, 250 mL 1
Funnel, micro 1
Support stand with buret clamp 1
Water, deionized varies

Refer to Consumables and replacement items on page 4 for order information.

Sample collection
• Analyze the samples immediately. The samples cannot be preserved for later
analysis.
• Collect samples in clean glass or plastic bottles with tight-fitting caps. Completely fill
the bottle and immediately tighten the cap.
• Let the sample temperature decrease to 50 °C (122 °F) or less before analysis.
• Prevent agitation of the sample and exposure to air.

1
Test procedure

1. Select a sample volume 2. Fill a 10‑mL buret to the 3. Use a graduated cylinder 4. Pour the sample into a
and titrant from Table 1 zero mark with the titrant. or pipet1 to measure the clean, 250-mL Erlenmeyer
on page 3. sample volume from Table 1 flask.
on page 3.

5. If the sample volume is 6. Add the contents of one 7. Swirl to mix. 8. Add 1 mL of Starch
less than 50 mL, dilute to Dissolved Oxygen 3 Powder Indicator Solution.
approximately 50 mL with Pillow.
deionized water.

9. Swirl to mix. 10. Put the flask under the 11. Use the multiplier in
buret. Swirl the flask. Add Table 1 on page 3 to
titrant until the color calculate the concentration.
changes to a permanent mL of titrant × multiplier =
blue color. mg/L sulfite SO32–.

Sample volumes and multipliers

Select a range in Table 1, then read across the table row to find the applicable
information for this test. Use the multiplier to calculate the concentration in the test
procedure.

1 Titration accuracy has a direct relation to the accuracy of the sample volume measurement. For smaller
volumes, it is recommended to use a pipet to increase accuracy.

2 Sulfite (500 mg/L)

 Example: A 50-mL sample was titrated with 0.0125 N titrant and 6 mL of titrant was used
at the endpoint. The concentration is 6 mL × 10 = 60 mg/L sulfite SO32–.
Table 1 Sample volumes and multipliers
Range (mg/L) Sample volume (mL) Titrant—potassium iodide-iodate Multiplier
0–100 50 0.0125 N 10
40–200 25 0.0125 N 20
100–500 10 0.0125 N 50
More than 500 5 0.0125 N 100

Conversions
To change the units or chemical form of the test result, multiply the test result by the
factor in Table 2.
Table 2 Conversions
mg/L sulfite (SO3 2–) to... multiply by: Example
mg/L bisulfite, hydrogen sulfite (HSO3–) 1.01 200 mg/L SO32– x 1.01 = 202 mg/L HSO3–
mg/L sodium bisulfite, sodium hydrogen sulfite (NaHSO3) 1.30 200 mg/L SO32– x 1.30 = 260 mg/L NaHSO3
mg/L sodium metabisulfite, sodium pyrosulfite (Na2S2O5) 2.37 200 mg/L SO32– x 2.37 = 474 mg/L Na2S2O5
mg/L sodium sulfite (Na2SO3) 1.58 200 mg/L SO32– x 1.58 = 316 mg/L Na2SO3

Interferences
Table 3 shows the substances that can interfere with this test.
Table 3 Interferences
Interfering substance Interference level
Metals Some metals, especially copper, catalyze the oxidation of sulfite to sulfate. Immediately add one
Dissolved Oxygen 3 Powder Pillow for each liter of sample during sample collection to prevent the
interference.
Nitrite Reacts with sulfite and causes low results.
Organic compounds Oxidizable organic compounds can cause high results.
Oxidizable compounds Cause high results.
Sulfide Causes high results.

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:
• Sulfite Voluette Ampule Standard, 5,000-mg/L SO32–
• 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 mL of titrant added.
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 mL of titrant added.
6. Add one more 0.1-mL addition of the standard solution to the titrated sample.

Sulfite (500 mg/L) 3

 7. Titrate the spiked sample to the endpoint. Record the mL of titrant added.
8. Compare the actual result to the correct result. The correct result for this titration is
1.0 mL of titrant 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:
• Sodium Thiosulfate Standard Solution, 0.025 N
• 250-mL volumetric flask, Class A
• 10.0-mL volumetric pipet, Class A and pipet filler safety bulb
• Deionized water

1. Prepare a 40-mg/L sulfite-equivalent standard solution as follows:

a. Use a pipet to add 10.0 mL of a 0.025 N sodium thiosulfate standard solution to
the volumetric flask.
b. Dilute to the mark with deionized water. Mix well. Prepare this solution daily.
2. Use the test procedure to measure the concentration of the prepared standard
solution. Use 50 mL of the prepared standard solution.
3. Compare the actual result to the correct result. If much more or less titrant was used,
there can be a problem with user technique, reagents or apparatus.

Summary of Method
The water sample is acidified and titrated with a potassium iodide-iodate standard
solution. The acid releases free iodine, which is reduced to colorless iodide by the sulfite
in the sample. When all of the sulfite is gone, the iodine reacts with the starch indicator to
form a blue color.
Consumables and replacement items
Required reagents

Description Quantity/Test Unit Item no.

Sulfite Reagent Set (approximately 100 tests): — each 2459800

Dissolved Oxygen 3 Reagent Powder Pillows 1 100/pkg 98799
Potassium Iodide-Iodate Standard Solution, 0.0125 N varies 1L 1400153
Starch Indicator Solution 1 mL 100 mL MDB 34932
Water, deionized varies 4L 27256

Required apparatus

Description Quantity/test Unit Item no.

Buret clamp, double 1 each 32800

Buret, Class A, 10 mL 1 each 2636538
Support stand 1 each 56300
Funnel, micro 1 each 2584335
Graduated cylinders—Select one or more for the sample volume:
Cylinder, graduated, 5 mL 1 each 50837
Cylinder, graduated, 10 mL 1 each 50838

4 Sulfite (500 mg/L)

Required apparatus (continued)
Description Quantity/test Unit Item no.

Cylinder, graduated, 25 mL 1 each 50840

Cylinder, graduated, 50 mL 1 each 50841
Cylinder, graduated, 100 mL 1 each 50842
®
Tensette pipets and pipet tips—Select one or more for the sample volume:
®
Pipet, TenSette , 0.1–1.0 mL 1 each 1970001
®
Pipet tips, TenSette Pipet, 0.1–1.0 mL varies 50/pkg 2185696
®
Pipet, TenSette , 1.0–10.0 mL 1 each 1970010
®
Pipet tips, TenSette Pipet, 1.0–10.0 mL varies 50/pkg 2199796
Flask, Erlenmeyer, 250 mL 1 each 50546

Recommended standards

Description Unit Item no.

Sulfite Equivalent Standard Solution, 10-mL Voluette® Ampule, 5,000-mg/L as SO32– 16/pkg 2267410
Sulfite Equivalent Standard Solution, 15 mg/L as SO32– 500 mL 2408449
Sodium Thiosulfate Standard Solution, 0.025 N 1L 2409353

Optional reagents and apparatus

Description Unit Item no.

®
Ampule Breaker, 10-mL Voluette Ampules each 2196800
Flask, volumetric, Class A, 250 mL each 1457446
Pipet, volumetric, Class A, 10 mL each 1451538
Pipet filler, safety bulb each 1465100
Sulfuric Acid Standard Solution, 19.2 N 100 mL 203832

Sulfite (500 mg/L) 5

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