ALKALINITY (2320)/Titration Method 2-27

2320 ALKALINITY*

2320 A. Introduction

1. Discussion contributions from borates, phosphates, silicates, or other bases

if these are present. Alkalinity in excess of alkaline earth metal
Alkalinity of a water is its acid-neutralizing capacity. It is the concentrations is significant in determining the suitability of a
sum of all the titratable bases. The measured value may vary water for irrigation. Alkalinity measurements are used in the
significantly with the end-point pH used. Alkalinity is a measure interpretation and control of water and wastewater treatment
of an aggregate property of water and can be interpreted in terms processes. Raw domestic wastewater has an alkalinity less than,
of specific substances only when the chemical composition of or only slightly greater than, that of the water supply. Properly
the sample is known. operating anaerobic digesters typically have supernatant alkalin-
Alkalinity is significant in many uses and treatments of natural ities in the range of 2000 to 4000 mg calcium carbonate
waters and wastewaters. Because the alkalinity of many surface (CaCO3)/L.1
waters is primarily a function of carbonate, bicarbonate, and
hydroxide content, it is taken as an indication of the concentra- 2. Reference
tion of these constituents. The measured values also may include
1. POHLAND, F.G. & D.E. BLOODGOOD. 1963. Laboratory studies on
mesophilic and thermophilic anaerobic sludge digestion. J. Water
* Approved by Standard Methods Committee, 1997. Pollut. Control Fed. 35:11.

2320 B. Titration Method

1. General Discussion hydrogen ion concentration, a simple extrapolation can be made

to the equivalence point.1,2
a. Principle: Hydroxyl ions present in a sample as a result of b. End points: When alkalinity is due entirely to carbonate or
dissociation or hydrolysis of solutes react with additions of bicarbonate content, the pH at the equivalence point of the
standard acid. Alkalinity thus depends on the end-point pH used. titration is determined by the concentration of carbon dioxide
For methods of determining inflection points from titration (CO2) at that stage. CO2 concentration depends, in turn, on the
curves and the rationale for titrating to fixed pH end points, see total carbonate species originally present and any losses that may
Section 2310B.1a. have occurred during titration. The pH values in Table 2320:I are
For samples of low alkalinity (less than 20 mg CaCO3/L) use suggested as the equivalence points for the corresponding alka-
an extrapolation technique based on the near proportionality of linity concentrations as milligrams CaCO3 per liter. “Phenol-
concentration of hydrogen ions to excess of titrant beyond the phthalein alkalinity” is the term traditionally used for the quan-
equivalence point. The amount of standard acid required to tity measured by titration to pH 8.3 irrespective of the colored
reduce pH exactly 0.30 pH unit is measured carefully. Because indicator, if any, used in the determination. Phenolphthalein or
this change in pH corresponds to an exact doubling of the metacresol purple may be used for alkalinity titration to pH 8.3.
Bromcresol green or a mixed bromcresol green-methyl red in-
dicator may be used for pH 4.5.
TABLE 2320:I END-POINT PH VALUES
c. Interferences: Soaps, oily matter, suspended solids, or
End Point pH precipitates may coat the glass electrode and cause a sluggish
Total Phenolphthalein response. Allow additional time between titrant additions to
Test Condition Alkalinity Alkalinity let electrode come to equilibrium or clean the electrodes
occasionally. Do not filter, dilute, concentrate, or alter sam-
Alkalinity, ple.
mg CaCO3/L:
d. Selection of procedure: Determine sample alkalinity from
30 4.9 8.3
150 4.6 8.3 volume of standard acid required to titrate a portion to a desig-
500 4.3 8.3 nated pH taken from ¶ 1b. Titrate at room temperature with a
Silicates, phosphates known properly calibrated pH meter or electrically operated titrator, or
or suspected 4.5 8.3 use color indicators. If using color indicators, prepare and titrate
Routine or automated an indicator blank.
analyses 4.5 8.3 Report alkalinity less than 20 mg CaCO3/L only if it has been
Industrial waste or complex determined by the low-alkalinity method of ¶ 4d.
system 4.5 8.3
Construct a titration curve for standardization of reagents.
2-28 PHYSICAL & AGGREGATE PROPERTIES (2000)

Color indicators may be used for routine and control titrations 4. Procedure
in the absence of interfering color and turbidity and for prelim-
inary titrations to select sample size and strength of titrant (see a. Color change: See Section 2310B.4b.
below). b. Potentiometric titration curve: Follow the procedure for
e. Sample size: See Section 2310B.1e for selection of size determining acidity (Section 2310B.4c), substituting the appro-
sample to be titrated and normality of titrant, substituting 0.02N priate normality of standard acid solution for standard NaOH,
or 0.1N sulfuric (H2SO4) or hydrochloric (HCl) acid for the and continue titration to pH 4.5 or lower. Do not filter, dilute,
standard alkali of that method. For the low-alkalinity method, concentrate, or alter the sample.
titrate a 200-mL sample with 0.02N H2SO4 from a 10-mL buret. c. Potentiometric titration to preselected pH: Determine the
f. Sampling and storage: See Section 2310B.1f. appropriate end-point pH according to ¶ 1b. Prepare sample and
titration assembly (Section 2310B.4c). Titrate to the end-point
2. Apparatus pH without recording intermediate pH values and without undue
delay. As the end point is approached make smaller additions of
See Section 2310B.2. acid and be sure that pH equilibrium is reached before adding
more titrant.
d. Potentiometric titration of low alkalinity: For alkalinities
3. Reagents less than 20 mg/L titrate 100 to 200 mL according to the
procedure of ¶ 4c, above, using a 10-mL microburet and 0.02N
a. Sodium carbonate solution, approximately 0.05N: Dry 3 to standard acid solution. Stop the titration at a pH in the range 4.3
5 g primary standard Na2CO3 at 250°C for 4 h and cool in a to 4.7 and record volume and exact pH. Carefully add additional
desiccator. Weigh 2.5 ⫾ 0.2 g (to the nearest mg), transfer to a titrant to reduce the pH exactly 0.30 pH unit and again record
1-L volumetric flask, fill flask to the mark with distilled water, volume.
and dissolve and mix reagent. Do not keep longer than 1 week.
b. Standard sulfuric acid or hydrochloric acid, 0.1N: Prepare 5. Calculations
acid solution of approximate normality as indicated under Prep-
aration of Desk Reagents. Standardize against 40.00 mL 0.05N a. Potentiometric titration to end-point pH:
Na2CO3 solution, with about 60 mL water, in a beaker by
titrating potentiometrically to pH of about 5. Lift out electrodes, A ⫻ N ⫻ 50 000
rinse into the same beaker, and boil gently for 3 to 5 min under Alkalinity, mg CaCO3/L ⫽
mL sample
a watch glass cover. Cool to room temperature, rinse cover glass
into beaker, and finish titrating to the pH inflection point. Cal-
where:
culate normality:
A ⫽ mL standard acid used and
N ⫽ normality of standard acid
or
Normality, N ⫽ A⫻B
53.00 ⫻ C
A ⫻ t ⫻ 1000
where: Alkalinity, mg CaCO3/L ⫽
mL sample
A ⫽ g Na2CO3 weighed into 1-L flask,
B ⫽ mL Na2CO3 solution taken for titration, and
C ⫽ mL acid used.
where:
t ⫽ titer of standard acid, mg CaCO3/mL.
Use measured normality in calculations or adjust to 0.1000N;
Report pH of end point used as follows: “The alkalinity to pH
1 mL 0.1000N solution ⫽ 5.00 mg CaCO3.
⫽ mg CaCO3/L” and indicate clearly if this pH
c. Standard sulfuric acid or hydrochloric acid, 0.02N: Dilute
corresponds to an inflection point of the titration curve.
200.00 mL 0.1000N standard acid to 1000 mL with distilled or
b. Potentiometric titration of low alkalinity:
deionized water. Standardize by potentiometric titration of 15.00
mL 0.05N Na2CO3 according to the procedure of ¶ 3b; 1 mL ⫽
1.00 mg CaCO3. Total alkalinity, mg CaCO3/L
d. Bromcresol green indicator solution, pH 4.5 indicator: 共2 B ⫺ C) ⫻ N ⫻ 50 000
Dissolve 100 mg bromcresol green, sodium salt, in 100 mL ⫽
mL sample
distilled water.
e. Mixed bromcresol green-methyl red indicator solution:3
where:
Use either the aqueous or the alcoholic solution:
B ⫽ mL titrant to first recorded pH,
1) Dissolve 100 mg bromcresol green sodium salt and 20 mg
C ⫽ total mL titrant to reach pH 0.3 unit lower, and
methyl red sodium salt in 100 mL distilled water. N ⫽ normality of acid.
2) Dissolve 100 mg bromcresol green and 20 mg methyl red in
100 mL 95% ethyl alcohol or isopropyl alcohol. c. Calculation of alkalinity relationships: The results obtained
f. Metacresol purple indicator solution, pH 8.3 indicator: from the phenolphthalein and total alkalinity determinations
Dissolve 100 mg metacresol purple in 100 mL water. offer a means for stoichiometric classification of the three prin-
g. Phenolphthalein solution, alcoholic, pH 8.3 indicator. cipal forms of alkalinity present in many waters. The classifica-
h. Sodium thiosulfate, 0.1N: See Section 2310B.3i. tion ascribes the entire alkalinity to bicarbonate, carbonate, and
ALKALINITY (2320)/Titration Method 2-29

TABLE 2320:II. ALKALINITY RELATIONSHIPS* 6. Precision and Bias

Hydroxide Carbonate Bicarbonate
Result of Alkalinity Alkalinity Concentration No general statement can be made about precision because
Titration as CaCO3 as CaCO3 as CaCO3 of the great variation in sample characteristics. The precision
of the titration is likely to be much greater than the uncer-
P ⫽ 0 0 0 T tainties involved in sampling and sample handling before the
P ⬍ ⁄T
12 0 2P T ⫺ 2P
P ⫽ 1⁄2T 0 2P 0
analysis.
P ⬎ 1⁄2T 2P ⫺ T 2(T ⫺ P) 0 In the range of 10 to 500 mg/L, when the alkalinity is due
P ⫽ T T 0 0 entirely to carbonates or bicarbonates, a standard deviation of 1
mg CaCO3/L can be achieved. Forty analysts in 17 laboratories
*Key: P⫺phenolphthalein alkalinity; T⫺total alkalinity.
analyzed synthetic samples containing increments of bicarbonate
equivalent to 120 mg CaCO3/L. The titration procedure of ¶ 4b
was used, with an end point pH of 4.5. The standard deviation
was 5 mg/L and the average bias (lower than the true value) was
hydroxide, and assumes the absence of other (weak) inorganic or 9 mg/L.5
organic acids, such as silicic, phosphoric, and boric acids. It Sodium carbonate solutions equivalent to 80 and 65 mg
further presupposes the incompatibility of hydroxide and bicar-
CaCO3/L were analyzed by 12 laboratories according to the
bonate alkalinities. Because the calculations are made on a
procedure of ¶ 4c.6 The standard deviations were 8 and 5
stoichiometric basis, ion concentrations in the strictest sense are
mg/L, respectively, with negligible bias.6 Four laboratories
not represented in the results, which may differ significantly
from actual concentrations especially at pH ⬎ 10. According to analyzed six samples having total alkalinities of about 1000
this scheme: mg CaCO3/L and containing various ratios of carbonate/
1) Carbonate (CO32⫺) alkalinity is present when phenolphtha- bicarbonate by the procedures of both ¶ 4a and ¶ 4c. The
lein alkalinity is not zero but is less than total alkalinity. pooled standard deviation was 40 mg/L, with negligible dif-
2) Hydroxide (OH⫺) alkalinity is present if phenolphthalein ference between the procedures.
alkalinity is more than half the total alkalinity.
3) Bicarbonate (HCO3⫺) alkalinity is present if phenol-
phthalein alkalinity is less than half the total alkalinity. These 7. References
relationships may be calculated by the following scheme,
where P is phenolphthalein alkalinity and T is total alkalinity 1. LARSON, T.E. & L.M. HENLEY. 1955. Determination of low alkalinity
(¶ 1b): or acidity in water. Anal. Chem. 27:851.
Select the smaller value of P or (T⫺P). Then, carbonate 2. THOMAS, J.F.J. & J.J. LYNCH. 1960. Determination of carbonate alka-
alkalinity equals twice the smaller value. When the smaller linity in natural waters. J. Amer. Water Works Assoc. 52:259.
value is P, the balance (T⫺2P) is bicarbonate. When the 3. COOPER, S.S. 1941. The mixed indicator bromocresol green-methyl
red for carbonates in water. Ind. Eng. Chem., Anal. Ed. 13:466.
smaller value is (T⫺P), the balance (2P⫺T) is hydroxide. All
4. JENKINS, S.R. & R.C. MOORE. 1977. A proposed modification to the
results are expressed as CaCO3. The mathematical conversion
classical method of calculating alkalinity in natural waters. J. Amer.
of the results is shown in Table 2320:II. (A modification of
Water Works Assoc. 69:56.
Table 2320:II that is more accurate when P ⯝ 1/2T has been 5. WINTER, J.A. & M.R. MIDGETT. 1969. FWPCA Method Study 1.
proposed.4) Mineral and Physical Analyses. Federal Water Pollution Control
Alkalinity relationships also may be computed nomo- Admin., Washington, D.C.
graphically (see Carbon Dioxide, Section 4500-CO2). Accu- 6. SMITH, R. 1980. Research Rep. No. 379, Council for Scientific and
rately measure pH, calculate OH⫺ concentration as milli- Industrial Research, South Africa.
grams CaCO3 per liter, and calculate concentrations of CO32⫺
and HCO3⫺ as milligrams CaCO3 per liter from the OH⫺
concentration, and the phenolphthalein and total alkalinities 8. Bibliography
by the following equations:
AMERICAN SOCIETY FOR TESTING AND MATERIALS. 1982. Standard Methods
⫺ for Acidity or Alkalinity of Water. Publ. D1067-70 (reapproved
CO3 2⫺
⫽ 2P ⫺ 2[OH ]
1977), American Soc. Testing & Materials, Philadelphia, Pa.
SKOUGSTAD M.W., M.J. FISHMAN, L.C. FRIEDMAN, D.E. ERDMAN, & S.S.
HCO3⫺ ⫽ T ⫺ 2P ⫹ [OH⫺]
DUNCAN. 1979. Methods for determination of inorganic substances
in water and fluvial sediments. In Techniques of Water-Resources
Similarly, if difficulty is experienced with the phenolphtha- Investigation of the United States Geological Survey. U.S. Geolog-
lein end point, or if a check on the phenolphthalein titration is ical Survey, Book 5, Chapter A1, Washington, D.C.
desired, calculate phenolphthalein alkalinity as CaCO3 from
the results of the nomographic determinations of carbonate
and hydroxide ion concentrations:

P ⫽ 1/2 [CO32⫺] ⫹ [OH⫺]