4500-Cl⫺ CHLORIDE*
4500-Cl⫺ A. Introduction
1. Occurrence largely a matter of personal preference. The argentometric
method (4500-Cl⫺.B) is suitable for use in relatively clear waters
Chloride, in the form of chloride (Cl⫺) ion, is one of the major when 0.15 to 10 mg Cl⫺ are present in the portion titrated. The
inorganic anions in water and wastewater. The salty taste pro- endpoint of the mercuric nitrate method (4500-Cl⫺.C) is easier to
duced by chloride concentrations is variable and dependent on detect. The potentiometric method (4500-Cl⫺.D) is suitable for
the chemical composition of water. Some waters containing colored or turbid samples in which color-indicated endpoints might
250 mg Cl⫺/L may have a detectable salty taste if the cation is be difficult to observe. The potentiometric method can be used
sodium. On the other hand, the typical salty taste may be absent without a pretreatment step for samples containing ferric ions (if not
in waters containing as much as 1000 mg/L when the predom- present in an amount greater than the chloride concentration), chro-
inant cations are calcium and magnesium. mic, phosphate, and ferrous and other heavy-metal ions. The ferri-
The chloride concentration is higher in wastewater than in raw cyanide method (4500-Cl⫺.E) is an automated technique. Flow
water because sodium chloride (NaCl) is a common article of injection analysis (4500-Cl⫺.G), an automated colorimetric tech-
diet and passes unchanged through the digestive system. Along nique, is useful for analyzing large numbers of samples. Preferably
the sea coast, chloride may be present in high concentrations determine chloride by ion chromatography (Section 4110). Chloride
because of leakage of salt water into the sewerage system. It also also can be determined by the capillary ion electrophoresis method
may be increased by industrial processes. (Section 4140). Methods 4500-Cl⫺.C and G in which mercury, a
A high chloride content may harm metallic pipes and struc- highly toxic reagent, is used require special disposal practices to
tures, as well as growing plants. avoid improper sewage discharges. Follow appropriate regulatory
procedures (see Section 1090).
2. Selection of Method
Six methods are presented for the determination of chloride.
3. Sampling and Storage
Because the first two are similar in most respects, selection is
Collect representative samples in clean, chemically resistant
glass or plastic bottles. The maximum sample portion required is
* Approved by Standard Methods Committee, 1997. Editorial revisions, 2011.
Joint Task Group: 20th Edition (4500-Cl⫺.G)—Scott Stieg (chair), Bradford R. 100 mL. No special preservative is necessary if the sample is to
Fisher, Owen B. Mathre, Theresa M. Wright. be stored.
4500-Cl⫺ B. Argentometric Method
1. General Discussion 3. Reagents
a. Principle: In a neutral or slightly alkaline solution, potas- a. Potassium chromate indicator solution: Dissolve 50 g
sium chromate can indicate the endpoint of the silver nitrate K2CrO4 in a little distilled water. Add AgNO3 solution until a
titration of chloride. Silver chloride is precipitated quantitatively definite red precipitate is formed. Let stand 12 h, filter, and dilute
before red silver chromate is formed. to 1 L with distilled water.
b. Interference: Substances in amounts normally found in b. Standard silver nitrate titrant, 0.0141M (0.0141N): Dis-
potable waters will not interfere. Bromide, iodide, and cyanide solve 2.395 g AgNO3 in distilled water and dilute to 1000 mL.
register as equivalent chloride concentrations. Sulfide, thiosul- Standardize against NaCl by the procedure described in
fate, and sulfite ions interfere but can be removed by treatment 4500-Cl⫺.B.4b; 1.00 mL ⫽ 500 g Cl⫺. Store in a brown bottle.
with hydrogen peroxide. Orthophosphate in excess of 25 mg/L c. Standard sodium chloride, 0.0141M (0.0141N): Dissolve
interferes by precipitating as silver phosphate. Iron in excess of 824.0 mg NaCl (dried at 140°C) in distilled water and dilute to
10 mg/L interferes by masking the endpoint. 1000 mL; 1.00 mL ⫽ 500 g Cl⫺.
d. Special reagents for removal of interference:
1) Aluminum hydroxide suspension—Dissolve 125 g alumi-
2. Apparatus num potassium sulfate or aluminum ammonium sulfate,
AlK(SO4)2 䡠 12H2O or AlNH4(SO4)2 䡠 12H2O, in 1 L distilled
a. Erlenmeyer flask, 250-mL. water. Warm to 60°C and add 55 mL conc ammonium hydroxide
b. Buret, 50-mL. (NH4OH) slowly with stirring. Let stand about 1 h, transfer to a
https://doi.org/10.2105/SMWW.2882.079 1
CHLORIDE (4500-Cl⫺)/Mercuric Nitrate Method
large bottle, and wash precipitate by successive additions, with where:
thorough mixing and decanting with distilled water, until free A ⫽ mL titration for sample,
from chloride. When freshly prepared, the suspension occupies a B ⫽ mL titration for blank, and
volume of approximately 1 L. N ⫽ normality of AgNO3.
2) Phenolphthalein indicator solution.
3) Sodium hydroxide (NaOH), 1N.
4) Sulfuric acid (H2SO4), 1N. mg NaCl/L ⫽ (mg Cl⫺/L) ⫻ 1.65
5) Hydrogen peroxide (H2O2), 30%.
4. Procedure 6. Precision and Bias
a. Sample preparation: Use a 100-mL sample or a suitable
A synthetic sample containing 241 mg Cl⫺/L, 108 mg Ca/L,
portion diluted to 100 mL. If the sample is highly colored, add
82 mg Mg/L; 3.1 mg K/L, 19.9 mg Na/L, 1.1 mg NO3⫺-N/L,
3 mL Al(OH)3 suspension, mix, let settle, and filter.
0.25 mg NO2⫺- N/L, 259 mg SO42⫺/L, and 42.5 mg total
If sulfide, sulfite, or thiosulfate is present, add 1 mL H2O2 and
alkalinity/L (contributed by NaHCO3) in distilled water was
stir for 1 min.
analyzed in 41 laboratories by the argentometric method, with
b. Titration: Directly titrate samples in the pH range 7 to 10.
a relative standard deviation of 4.2% and a relative error of
Adjust sample pH to 7 to 10 with H2SO4 or NaOH if it is not in this
1.7%.
range. For adjustment, preferably use a pH meter with a non-
chloride-type reference electrode. (If only a chloride-type electrode
is available, determine amount of acid or alkali needed for adjust-
7. Bibliography
ment and discard this sample portion. Treat a separate portion with
required acid or alkali and continue analysis.) Add 1.0 mL K2CrO4
indicator solution. Titrate with standard AgNO3 titrant to a pinkish HAZEN, A. 1889. On the determination of chlorine in water. Amer. Chem.
yellow endpoint. Be consistent in endpoint recognition. J. 11:409.
KOLTHOFF, I.M. & V.A. STENGER. 1947. Volumetric Analysis, 2nd ed.
Standardize AgNO3 titrant and establish reagent blank value by
Vol. 2; pp. 242–245, 256 –258. Interscience Publishers, New York,
the titration method outlined above. A blank of 0.2 to 0.3 mL is usual. N.Y.
PAUSTIAN, P. 1987. A novel method to calculate the Mohr chloride
5. Calculation titration. In Advances in Water Analysis and Treatment, Proc. 14th
Annu. AWWA Water Quality Technology Conf., November 16 –
20, 1986, Portland, Ore., p. 673. American Water Works Assoc.,
(A ⫺ B) ⫻ N ⫻ 35 450
mg Cl⫺/L ⫽ Denver, Colo.
mL sample
4500-Cl⫺ C. Mercuric Nitrate Method
1. General Discussion 2. Apparatus
a. Principle: Chloride can be titrated with mercuric nitrate, a. Erlenmeyer flask, 250-mL.
Hg(NO3)2, because of the formation of soluble, slightly dis- b. Microburet, 5-mL with 0.01-mL graduation intervals.
sociated mercuric chloride. In the pH range 2.3 to 2.8, diphe-
nylcarbazone indicates the titration endpoint by formation of
3. Reagents
a purple complex with the excess mercuric ions. Xylene
cyanol FF serves as a pH indicator and endpoint enhancer.
Increasing the strength of the titrant and modifying the indi- a. Standard sodium chloride, 0.0141M (0.0141N): See
cator mixtures extend the range of measurable chloride con- 4500-Cl⫺.B.3c.
centrations. b. Nitric acid (HNO3), 0.1N.
c. Sodium hydroxide (NaOH), 0.1N.
b. Interference: Bromide and iodide are titrated with
d. Reagents for chloride concentrations below 100 mg/L:
Hg(NO3)2 in the same manner as chloride. Chromate, ferric, and
1) Indicator-acidifier reagent—The HNO3 concentration of
sulfite ions interfere when present in excess of 10 mg/L. this reagent is an important factor in the success of the
c. Quality control (QC): The QC practices considered to be determination and can be varied as indicated in ¶ a) or b)
an integral part of each method are summarized in Table below to suit the alkalinity range of the sample. Reagent a)
4020:I. contains sufficient HNO3 to neutralize a total alkalinity of
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