2310 Acidity
2310 Acidity
2310 Acidity
Acidity
Approved by Standard Methods Committee, 1997. Editorial revisions, 2011 and 2020.
2310 A. Introduction
Acidity of a water is its quantitative capacity to react with a strong carbonic and acetic, and hydrolyzing salts such as iron or alumi-
base to a designated pH. The measured value may vary signifi- num sulfates may contribute to the measured acidity according to
cantly with the endpoint pH used in the determination. Acidity is the method of determination.
a measured aggregate property of water and can be interpreted in Acids contribute to corrosiveness and influence chemical reac-
terms of specific substances only when the chemical composition tion rates, chemical speciation, and biological processes. The mea-
of the sample is known. Strong mineral acids, weak acids such as surement also reflects a change in the quality of the source water.
https://doi.org/10.2105/SMWW.2882.022 1
2310 ACIDITY - B. Titration Method
available chlorine in the sample may bleach the indicator. Elimi- e. Flasks, volumetric, 1000-, 200-, 100-mL.
nate this source of interference by adding 1 drop of 0.1 M sodium f. Burets, borosilicate glass, 50-, 25-, 10-mL.
thiosulfate (Na2S2O3). g. Polyolefin bottle, 1-L.
d. Selection of procedure: Determine sample acidity from the
volume of standard alkali required to titrate a portion to a pH of 3. Reagents
8.3 (phenolphthalein acidity) or pH 3.7 (methyl orange acidity of
wastewaters and grossly polluted waters). Titrate at room tem- a. Carbon dioxide-free water: Prepare all stock and standard
perature using a properly calibrated pH meter, electrically oper- solutions and dilution water for the standardization procedure with
ated titrator, or color indicators. reagent water that has been freshly boiled for 15 min and cooled
Use the hot peroxide procedure (2310 B.4a) to pretreat sam- to room temperature. The final pH of the water should be ≥6.0 and
ples known or suspected to contain hydrolyzable metal ions or its conductivity should be <2 μmhos/cm.
reduced forms of polyvalent cation, such as iron pickle liquors, b. Potassium hydrogen phthalate solution, approximately
acid mine drainage, and other industrial wastes. 0.05 N: Crush 15 to 20 g primary standard KHC8H4O4 to about
Color indicators may be used for routine and control titrations in 100 mesh and dry at 120 °C for 2 h. Cool in a desiccator. Weigh
the absence of interfering color and turbidity and for preliminary 10.0 ± 0.5 g (to the nearest mg), transfer to a 1-L volumetric flask,
titrations to select sample size and strength of titrant (2310 B.4b). and dilute to 1000 mL.
e. Sample size: The range of acidities found in wastewaters c. Standard sodium hydroxide titrant, 0.1 N: Prepare solution
is so large that a single sample size and normality of base used approximately 0.1 N as indicated under Preparation of Desk
as titrant cannot be specified. Use a sufficiently large volume Reagents. Standardize by titrating 40.00 mL KHC8H4O4 solu-
of titrant (20 mL or more from a 50-mL buret) to obtain rela- tion (3b), using a 25-mL buret. Titrate to the inflection point
tively good volumetric precision while keeping sample volume (2310 B.1a), which should be close to pH 8.7. Calculate normality
sufficiently small to permit sharp endpoints. For samples hav- of NaOH:
ing acidities less than about 1000 mg/L as calcium carbonate
(CaCO3), select a volume with less than 50 mg CaCO3 equiva- A×B
Normality =
lent acidity and titrate with 0.02 N sodium hydroxide (NaOH). 204.2 × C
For acidities greater than about 1000 mg/L as CaCO3, use a por-
tion containing acidity equivalent to less than 250 mg CaCO3 where:
and titrate with 0.1 N NaOH. If necessary, make a preliminary A = g KHC8H4O4 weighed into 1-L flask,
titration to determine optimum sample size and/or normality B = mL KHC8H4O4 solution taken for titration,
of titrant. C = mL NaOH solution used, and
f. Sampling and storage: Collect samples in polyethylene or 204.2 = equivalent weight of KHC8H4O4.
borosilicate glass bottles and store at a low temperature. Fill bot-
tles completely and cap tightly. Because waste samples may be Use the measured normality in further calculations or adjust to
subject to microbial action and to loss or gain of CO2 or other 0.1000 N; 1 mL = 5.00 mg CaCO3.
gases when exposed to air, analyze samples without delay, prefer- d. Standard sodium hydroxide titrant, 0.02 N: Dilute 200 mL
ably within 1 d. If biological activity is suspected analyze within 0.1 N NaOH to 1000 mL and store in a polyolefin bottle protected
6 h. Avoid sample agitation and prolonged exposure to air. from atmospheric CO2 by a soda lime tube or tight cap. Standard-
g. Quality control (QC): The QC practices considered to be an ize against KHC8H4O4 as directed in paragraph c above, using
integral part of each method are summarized in Tables 2020:1 and 15.00 mL KHC8H4O4 solution and a 50-mL buret. Calculate nor-
Table 2020:2. mality (¶ c above); 1 mL = 1.00 mg CaCO3.
e. Hydrogen peroxide (H2O2), 30%.
2. Apparatus f. Bromophenol blue indicator solution, pH 3.7 indicator: Dis-
solve 100 mg bromophenol blue, sodium salt, in 100 mL water.
a. Electrometric titrator: Use any commercial pH meter or g. Metacresol purple indicator solution, pH 8.3 indicator: Dis-
electrically operated titrator that uses a glass electrode and can be solve 100 mg metacresol purple in 100 mL water.
read to 0.05 pH unit. Standardize and calibrate according to the h. Phenolphthalein indicator solution, alcoholic, pH 8.3 indicator.
manufacturer’s instructions. Pay special attention to temperature i. Sodium thiosulfate, 0.1 M: Dissolve 25 g Na2S2O3 · 5H2O and
compensation and electrode care. If automatic temperature com- dilute to 1000 mL with reagent water.
pensation is not provided, titrate at 25 ± 5 °C.
b. Titration vessel: The size and form depends on the electrodes 4. Procedure
and the sample size. Keep the free space above the sample as
small as practicable, but allow room for titrant and full immersion If sample is free from hydrolyzable metal ions and reduced
of the indicating portions of electrodes. For conventional-sized forms of polyvalent cations, proceed with analysis according to
electrodes, use a 200-mL, tall-form Berzelius beaker without a paragraph’s b, c, or d below. If a sample is known or suspected to
spout. Fit the beaker with a stopper having 3 holes, to accommo- contain such substances, pretreat according to paragraph a below.
date the 2 electrodes and the buret. With a miniature combination a. Hot peroxide treatment: Pipet a suitable sample (see
glass-reference electrode use a 125-mL or 250-mL Erlenmeyer 2310 B.1e) into titration flasks. Measure pH. If pH is above 4.0
flask with a 2-hole stopper. add 5-mL increments of 0.02 N sulfuric acid (H2SO4) (Section
c. Magnetic stirrer. 2320 B.3c) to reduce pH to 4 or less. Remove electrodes. Add 5
d. Pipets, volumetric. drops 30% H2O2 and boil for 2 to 5 min. Cool to room temperature
https://doi.org/10.2105/SMWW.2882.022 2
2310 ACIDITY - B. Titration Method
and titrate with standard alkali to pH 8.3 according to the proce- where:
dure of paragraph d below.
A = mL NaOH titrant used,
b. Color change: Select the sample size and normality of
B = normality of NaOH,
titrant according to criteria of 2310 B.1e. Adjust the sample C = mL H2SO4 used (2310 B.4a),
to room temperature, if necessary, and with a pipet discharge D = normality of H2SO4, and
sample into an Erlenmeyer flask, while keeping the pipet tip 50 000 = equivalent weight of CaCO3.
near the flask bottom. If free residual chlorine is present add
0.05 mL (1 drop) 0.1 M Na2S2O3 solution, or destroy with ultra- Report the pH of the endpoint used, as follows: “The acidity to
violet radiation. Add 0.2 mL (5 drops) indicator solution and pH ____ = ____ mg/L as CaCO3.” If a negative value is obtained,
titrate over a white surface to a persistent color change charac- report the value as negative. The absolute value of this negative
teristic of the equivalence point. Commercial indicator solutions value should be equivalent to the net alkalinity.
or solids designated for the appropriate pH range (3.7 or 8.3)
may be used. Check the color at the endpoint by adding to the 6. Precision and Bias
buffer solution the same concentration of indicator used with the
sample at the designated pH. No general statement can be made about precision because
c. Potentiometric titration curve: of the great variation in sample characteristics. The precision of
1) Rinse the electrodes and titration vessel with reagent water the titration is likely to be much greater than the uncertainties
and drain. Select the sample size and normality of titrant accord- involved in sampling and sample handling before analysis.
ing to the criteria of 2310 B.1e. Adjust the sample to room tem- Forty analysts in 17 laboratories analyzed synthetic water sam-
perature, if necessary, and with a pipet discharge sample while ples containing increments of bicarbonate equivalent to 20 mg/L
keeping the pipet tip near the titration vessel bottom. CaCO3. Titration according to the procedure of 2310 B.4d gave a
2) Measure the sample pH. Add standard alkali in increments standard deviation of 1.8 mg/L CaCO3, with negligible bias. Five
of 0.5 mL or less, such that a change of less than 0.2 pH units laboratories analyzed 2 samples containing sulfuric, acetic, and for-
occurs per increment. After each addition, mix thoroughly mic acids and aluminum chloride by the procedures of 2310 B.4b
but gently with a magnetic stirrer. Avoid splashing. Record and 4d. The mean acidity of one sample (to pH 3.7) was 487 mg/L
pH when a constant reading is obtained. Continue adding the CaCO3, with a standard deviation of 11 mg/L. The bromophenol
titrant and measure pH until pH 9 is reached. Construct the blue titration of the same sample was 90 mg/L greater, with a stan-
titration curve by plotting observed pH values versus cumula- dard deviation of 110 mg/L. The other sample had a potentiometric
tive milliliters of titrant added. A smooth curve showing one or titration of 547 mg/L, with a standard deviation of 54 mg/L, while
more inflections should be obtained. A ragged or erratic curve the corresponding indicator result was 85 mg/L greater, with a stan-
may indicate that equilibrium was not reached between succes- dard deviation of 56 mg/L. The major difference between the sam-
sive alkali additions. Determine acidity relative to a particular ples was the substitution of ferric ammonium citrate, in the second
pH from the curve. sample, for part of the aluminum chloride.
d. Potentiometric titration to pH 3.7 or 8.3: Prepare the sample
and titration assembly as specified in paragraph c1 above. Titrate Bibliography
to the preselected endpoint pH (2310 B.1b) without recording
intermediate pH values. As the endpoint is approached make Winter JA, Midgett MR. FWPCA Method Study 1: Mineral and physical
smaller additions of alkali and be sure that pH equilibrium is analyses. Washington DC: Federal Water Pollution Control Admini
reached before making the next addition. stration; 1969.
Brown E, Skougstad MW, Fishman MJ. Methods for collection and analysis
5. Calculation of water samples for dissolved minerals and gases. Chapter A1 in Book
5, Techniques of Water-Resources Investigations of United States Geo-
(A × B) − (C× D) × 50 000 logical Survey. Washington DC: U.S. Geological Survey; 1970.
Acidity, as mg CACO3 /L = Snoeyink VL, Jenkins D. Water chemistry. New York (NY): John Wiley &
mL sample Sons, New York; 1980.