SULFITE (4500-SO32⫺)/Iodometric Method 4-183

4500-SO32⫺ SULFITE*

4500-SO32⫺ A. Introduction

1. Occurrence water treatment and discharge may be important environmen-

tally, principally because of its toxicity to fish and other aquatic
Sulfite ions (SO32⫺) may occur in boilers and boiler feedwa- life and its rapid oxygen demand.
ters treated with sulfite for dissolved oxygen control, in natural
waters or wastewaters as a result of industrial pollution, and in 2. Selection of Method
treatment plant effluents dechlorinated with sulfur dioxide (SO2).
Excess sulfite ion in boiler waters is deleterious because it lowers The iodometric titration method is suitable for relatively clean
the pH and promotes corrosion. Control of sulfite ion in waste- waters with concentrations above 2 mg SO32⫺/L. The phenan-
throline colorimetric determination, following evolution of sul-
fite from the sample matrix as SO2, is preferred for low levels of
*Approved by Standard Methods Committee, 2000. sulfite.

4500-SO32⫺ B. Iodometric Method

1. General Discussion results unless sulfamic acid is added to destroy nitrite. Addition
of EDTA as a complexing agent at the time of sample collection
a. Principle: An acidified sample containing sulfite (SO32⫺) is inhibits Cu2⫹ catalysis and promotes oxidation of ferrous to
titrated with a standardized potassium iodide-iodate titrant. Free ferric iron before analysis. Sulfide and thiosulfate ions normally
iodine, liberated by the iodide-iodate reagent, reacts with SO32⫺. would be expected only in samples containing certain industrial
The titration endpoint is signalled by the blue color resulting discharges, but must be accounted for if present. Sulfide may be
from the first excess of iodine reacting with a starch indicator. removed by adding about 0.5 g zinc acetate and analyzing the
b. Interferences: The presence of other oxidizable materials, supernatant of the settled sample. However, thiosulfate may have
such as sulfide, thiosulfate, and Fe2⫹ ions, can cause apparently to be determined by an independent method (e.g., the formalde-
high results for sulfite. Some metal ions, such as Cu2⫹, may hyde/iodometric method1), and then the sulfite determined by
catalyze the oxidation of SO32⫺ to SO42⫺ when the sample is difference.
exposed to air, thus leading to low results. NO2⫺ will react with c. Minimum detectable concentration: 2 mg SO32⫺/L.
SO32⫺ in the acidic reaction medium and lead to low sulfite
4-184 INORGANIC NONMETALS (4000)

2. Reagents 4. Calculation
(A ⫺ B) ⫻ M ⫻ 6 ⫻ 40 000
a. Sulfuric acid: H2SO4, 1 ⫹ 1. mg SO32⫺/L ⫽
b. Standard potassium iodide-iodate titrant, 0.002083M: Dis- mL sample
solve 0.4458 g primary-grade anhydrous KIO3 (dried for 4 h at where:
120°C), 4.35 g KI, and 310 mg sodium bicarbonate (NaHCO3) in A ⫽ mL titrant for sample,
distilled water and dilute to 1000 mL; 1.00 mL ⫽ 500 ␮g SO32⫺. B ⫽ mL titrant for blank, and
c. Sulfamic acid, NH2SO3H, crystalline. M ⫽ molarity of KI-KIO3 titrant.
d. EDTA reagent: Dissolve 2.5 g disodium EDTA in 100 mL
distilled water. 5. Precision and Bias
e. Starch indicator: To 5 g starch (potato, arrowroot, or
soluble) in a mortar, add a little cold distilled water and grind to Three laboratories analyzed five replicate portions of a stan-
a paste. Add mixture to 1 L boiling distilled water, stir, and let dard sulfite solution and of secondary treated wastewater effluent
settle overnight. Use clear supernatant. Preserve by adding either to which sulfite was added. The data are summarized below.
1.3 g salicylic acid, 4 g ZnCl2, or a combination of 4 g sodium Individual analyst’s precision ranged from 0.7 to 3.6% standard
propionate and 2 g sodium azide to 1 L starch solution. deviation (N ⫽ 45).
Standard Relative
Deviation, Standard
X ␴ Deviation
3. Procedure Sample mg/L mg/L %

Standard,
a. Sample collection: Collect a fresh sample, taking care to 6.3 mg SO32⫺/L 4.5 0. 25 5.5
minimize contact with air. Fix cooled samples (⬍50°C) imme- Secondary
diately by adding 1 mL EDTA solution/100 mL sample. Cool hot effluent with 2.1 0.28 13.4
samples to 50°C or below. Do not filter. 52.0 mg SO 2⫺/
3
b. Titration: Add 1 mL H2SO4 and 0.1 g NH2SO3H crystals to L
a 250-mL erlenmeyer flask or other suitable titration vessel. Secondary effluent
with
Accurately measure 50 to 100 mL EDTA-stabilized sample into
4.0 mg SO32⫺/L 3.6 0.17 4.8
flask, keeping pipet tip below liquid surface. Add 1 mL starch
indicator solution. Titrate immediately with standard KI-KIO3 6. Reference
titrant, while swirling flask, until a faint permanent blue color
develops. Analyze a reagent blank using distilled water instead 1. KURTENACKER, A. 1924. The aldehyde-bisulfite reaction in mass anal-
of sample. ysis. Z. Anal. Chem. 64:56.

4500-SO32⫺ C. Phenanthroline Method

1. General Discussion 3) Tubing connectors, quick-disconnect, polypropylene.

4) Tubing, flexible PVC, for use in all connections.
a. Principle: An acidified sample is purged with nitrogen 5) Nessler tube, 100-mL.
gas and the liberated SO2 is trapped in an absorbing solution b. Colorimetric equipment: One of the following is required:
containing ferric ion and 1,10-phenanthroline. Ferric iron is 1) Spectrophotometer, for use at 510 nm, providing a light
reduced to the ferrous state by SO2, producing the orange path of 1 cm or longer.
tris(1,10-phenanthroline) iron(II) complex. After excess ferric 2) Filter photometer, providing a light path of 1 cm or longer
iron is removed with ammonium bifluoride, the phenanthro- and equipped with a green filter having maximum transmittance
line complex is measured colorimetrically at 510 nm.1 near 510 nm.
b. Interferences: See Section 4500-SO32⫺.B.1b.
c. Minimum detectable concentration: 0.01 mg SO32⫺/L.
3. Reagents

2. Apparatus a. 1,10-phenanthroline solution, 0.03M: Dissolve 5.95 g 1,10-

phenanthroline in 100 mL 95% ethanol. Dilute to 1 L with
a. Apparatus for evolution of SO2: Figure 4500-SO32⫺:1 distilled water. Discard if solution becomes colored.
shows the following components: b. Ferric ammonium sulfate solution, 0.01M: Dissolve 4.82 g
1) Gas flow meter, with a capacity to measure 2 L/min of pure NH4Fe(SO4)2 䡠 12H2O in 1 L distilled water to which has been
nitrogen gas. added 1 mL conc H2SO4 to suppress ferric hydrolysis. Filter
2) Gas washing bottle, 250-mL, with coarse-porosity, 12- through a glass fiber filter if insoluble matter is visible. If
mm-diam fritted cylinder gas dispersion tube. necessary, adjust volume of acid so that a mixture of 10 parts of
SULFITE (4500-SO32⫺)/Phenanthroline Method 4-185

4. Procedure

a. Sample collection: Collect a fresh sample taking care to

minimize contact with air. Fix cooled samples (⬍50°C) imme-
diately by adding 1 mL EDTA solution for each 100 mL sample.
b. SO2 evolution: Prepare the absorbing solution by adding 5
mL 1,10-phenanthroline solution, 0.5 mL ferric ammonium sul-
fate solution, 25 mL distilled water, and 5 drops octyl alcohol (to
act as defoamer) to a 100-mL nessler tube; insert a gas dispersion
tube. Add 1 mL sulfamic acid solution to the gas washing bottle
and 100 mL of sample or a portion containing less than 100 ␮g
SO32⫺ diluted to 100 mL. Add 10 mL 1 ⫹ 1 HCl and immedi-
ately connect the gas washing bottle to the gas train as shown in
Figure 4500-SO32⫺:1. Place a spring or rubber band on the gas
washing bottle to keep the top securely closed during gas flow.
Figure 4500-SO32ⴚ:1. Apparatus for evolution of SO2 from samples for Adjust nitrogen flow to 2.0 L/min and purge for 60 min.
colorimetric analysis. c. Colorimetric measurement: After exactly 60 min, turn off
nitrogen flow, disconnect nessler tube, and immediately add 1 mL
ammonium bifluoride solution. Remove gas dispersion tube after
rinsing it with distilled water into the tube and forcing the rinse
phenanthroline solution and one part of ferric ammonium sulfate water into the nessler tube with a rubber bulb. Dilute to 50 mL in the
solution will have a pH between 5 and 6. nessler tube and mix by rapidly moving the tube in a circular
c. Ammonium bifluoride, 5%: Dissolve 25 g NH4HF2 in 500 motion. Do not let rubber stoppers or PVC tubing come in contact
mL distilled water. Store in a polyethylene bottle and dispense with the absorbing solution. After at least 5 min from the time of
with a plastic pipet. adding ammonium bifluoride, read the absorbance versus distilled
d. Potassium tetrachloromercurate (TCM), K2HgCl4, 0.04M: water at 510 nm using either a 5-cm cell for a range of 0 to 30 ␮g
Dissolve 10.86 g HgCl2, 5.96 g KCl, and 0.066 g disodium EDTA SO32⫺ per portion or a 1-cm cell for a range of 0 to 100 ␮g SO32⫺.
in distilled water and dilute to 1 L. Adjust pH to 5.2. This reagent Avoid transferring octyl alcohol into the cell by letting it rise to the
normally is stable for 6 months, but discard if a precipitate forms.2 surface of the absorbing solution and transferring the clear lower
e. Dilute TCM-stabilized sulfite standard: Dissolve 0.5 g Na2SO3 solution to the cell with a pipet. Make a calibration curve by
in 500 mL distilled water. Standardize on the day of preparation, but analyzing a procedure blank and at least three standards. Run at
wait at least 30 min to allow the rate of oxidation to slow. Determine least one standard with each set of samples. For maximum accuracy
hold samples and standards at the same temperature and keep the
molarity by titrating with standard 0.0125M potassium iodide-io-
time interval from start of purging to the addition of ammonium
date titrant using starch indicator (see Section 4500-SO32⫺.B). Cal-
bifluoride constant. This is easier to do if several gas trains are used
culate molarity of working standard as follows:
simultaneously in parallel. If ambient temperatures are subject to
frequent fluctuation, a water bath may be used to control color
(A ⫺ B)⫻M development at a fixed temperature.
Molarity of SO32⫺standard ⫽
mL sample
5. Calculation
where:
A ⫽ titrant for sample, mL, ␮g SO32⫺ from calibration curve
mg SO32⫺/L ⫽
B ⫽ titrant for blank, mL, mL sample
M ⫽ molarity of potassium iodide-iodate titrant.
6. Precision and Bias
Because stock Na2SO3 solution is unstable, immediately after
standardization, pipet 10 mL into a 500-mL volumetric flask Three laboratories analyzed five replicate portions of a standard
partially filled with TCM and dilute to mark with TCM. Calcu- sulfite solution and of secondary treated wastewater effluent to which
late the concentration of this dilute sulfite solution by multiply- sulfite was added. The data are summarized below. Individual analyst’s
ing the stock solution concentration by 0.02. This TCM-stabi- precision ranged from 4.1 to 10.5% standard deviation (N ⫽ 45).
lized standard is stable for 30 d if stored at 5°C. Discard as soon Standard Relative
as any precipitate is noticed at the bottom. Deviation, Standard
f. Standard potassium iodide-iodate titrant, 0.0125M: See X ␴ Deviation
Section 4500-SO32⫺.B.2b. Sample mg/L mg/L %
g. Hydrochloric acid, 1 ⫹ 1. Standard,
h. Octyl alcohol, reagent-grade. 4.7 mg SO32⫺/L 3.7 0.78 21
i. Sulfamic acid, 10%: Dissolve 10 g NH2SO3H in 100 mL Secondary effluent with
distilled water. This reagent can be kept for a few days if 0.12 mg SO32⫺/L 0.12 0.03 25
protected from air. Secondary effluent with
4.0 mg SO32⫺/L 3.7 0.30 8.0
j. EDTA reagent: See Section 4500-SO32⫺.B.2d.
4-186 INORGANIC NONMETALS (4000)

7. References 2. WEST, P.W. & G.C. GAEKE. 1956. Fixation of sulfur dioxide as
sulfitomercurate and subsequent colorimetric determination. Anal.
1. STEPHENS, B.G. & F. LINDSTROM. 1964. Spectrophotometric determi- Chem. 28:1816.
nation of sulfur dioxide suitable for atmospheric analysis. Anal.
Chem. 36:1308.