3500-Ca
CALCIUM
Approved by Standard Methods Committee, 1997. Editorial revisions, 2011 and 2020. Joint Task Group: 20th Edition—Brian J. Condike (chair), Deanna K. Anderson,
Anthony Bright, Richard A. Cahill, Alois F. Clary, C. Ellen Gonter, Peter M. Grohse, Daniel C. Hillman, Albert C. Holler, Amy Hughes, J. Charles Jennett, Roger A. Minear,
Marlene O. Moore, Gregg L. Oelker, S. Kusum Perera, James G. Poff, Jeffrey G. Skousen, Michael D. Wichman, John L. Wuepper.
3500-Ca A. Introduction
1. Occurrence and Significance
Calcium (Ca) is the third element in Group IIA of the periodic
table. It has an atomic number of 20, an atomic weight of 40.08,
and a valence of 2. The average abundance of Ca in the earth’s
crust is 4.9%; in soils it is 0.07 to 1.7%; in streams it is about
15 mg/L; and in groundwaters it is from 1 to >500 mg/L. The
most common forms of calcium are calcium carbonate (­calcite)
and calcium-magnesium carbonate (dolomite). Calcium com-
pounds are widely used in pharmaceuticals, photography, lime,
de-icing salts, pigments, fertilizers, and plasters. Calcium carbon-
ate solubility is controlled by pH and dissolved CO2. The CO2,
HCO3−, and CO32− equilibrium is the major buffering mecha-
nism in fresh waters. Hardness is based on the concentration of
­calcium and magnesium salts, and often is used as a measure of
potable water quality.
Calcium is necessary in plant and animal nutrition and is an
essential component of bones, shells, and plant structures. The
presence of calcium in water supplies results from passage over
deposits of limestone, dolomite, gypsum, and gypsiferous shale.
Small concentrations of calcium carbonate combat corrosion of
metal pipes by laying down a protective coating. Because pre-
cipitation of calcite in pipes and in heat-exchangers can cause
3500-Ca B. EDTA Titrimetric Method
1. General Discussion
a. Principle: When EDTA (ethylenediaminetetraacetic acid or
its salts) is added to water containing both calcium and magne-
sium, it combines first with the calcium. Calcium can be deter-
mined directly, with EDTA, when the pH is made sufficiently
high that the magnesium is largely precipitated as the hydroxide
and an indicator is used that combines with calcium only. Several
indicators give a color change when all of the calcium has been
complexed by the EDTA at a pH of 12 to 13.
b. Interference: Under conditions of this test, the following con-
centrations of ions cause no interference with the calcium hardness
determination: 2 mg/L Cu2+, 20 mg/L Fe2+, 20 mg/L Fe3+, 10 mg/L
Mn2+, 5 mg/L Zn2+, 5 mg/L Pb2+, 5 mg/L Al3+, and 5 mg/L Sn4+.
Orthophosphate precipitates calcium at the pH of the test. Strontium
and barium give a positive interference and alkalinity in excess of
300 mg/L may cause an indistinct endpoint in hard waters.
https://doi.org/10.2105/SMWW.2882.052
damage, the amount of calcium in domestic and industrial waters
is often controlled by water softening (e.g., ion exchange, reverse
osmosis). Calcium carbonate saturation and water hardness are
discussed in Sections 2330 and 2340, respectively.
Calcium contributes to the total hardness of water. Chemi-
cal softening treatment, reverse osmosis, electrodialysis, or ion
exchange is used to reduce calcium and the associated hardness.
2. Selection of Method
The atomic absorption methods (Sections 3111 B, D, and E)
and inductively coupled plasma method (Section 3120) are accu-
rate means of determining calcium. The EDTA titration method
(3500-Ca B) gives good results for control and routine applica-
tions, but for samples containing high P levels (>50 mg/L) only
the atomic absorption or atomic emission methods are recom-
mended because of interferences often encountered with EDTA
indicators.
3. Storage of Samples
The customary precautions are sufficient if care is taken to redis-
solve any calcium carbonate that may precipitate on standing.
c. Quality control (QC): The QC practices considered to be an
integral part of each method can be found in Section 3020.
2. Reagents
a. Sodium hydroxide (NaOH), 1 N.
b. Indicators: Many indicators are available for the calcium
titration. Some are described in the literature (3500-Ca B.6); oth-
ers are commercial preparations and also may be used. Murex-
ide (ammonium purpurate) was the first indicator available for
detecting the calcium endpoint; directions for its use are pre-
sented in this procedure. Individuals who have difficulty recog-
nizing the murexide endpoint may find the indicator Eriochrome
Blue Black R (color index number 202) or Solochrome Dark
Blue an improvement because of the color change from red to
pure blue. Eriochrome Blue Black R is sodium-1-(2-hydroxy-
1-­naphthylazo)-2-naphthol-4-sulfonic acid. Other indicators
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 3500-Ca CALCIUM - B. EDTA Titrimetric Method
s­ pecifically designed for use as endpoint detectors in EDTA titra-
tion of calcium may be used.
1) Murexide (ammonium purpurate) indicator—This indicator
changes from pink to purple at the endpoint. Prepare by dissolv-
ing 150 mg dye in 100 g absolute ethylene glycol. Water solutions
of the dye are not stable for longer than 1 d. A ground mixture of
dye powder and sodium chloride (NaCl) provides a stable form
of the indicator. Prepare by mixing 200 mg murexide with 100 g
solid NaCl and grinding the mixture to 40 to 50 mesh. Titrate
immediately after adding the indicator because it is unstable
under alkaline conditions. Facilitate endpoint recognition by pre-
paring a color comparison blank containing 2.0 mL NaOH solu-
tion, 0.2 g solid indicator mixture (or 1 to 2 drops if a solution is
used), and sufficient standard EDTA titrant (0.05 to 0.10 mL) to
produce an unchanging color.
2) Eriochrome Blue Black R indicator—Prepare a stable form
of the indicator by grinding together in a mortar 200 mg pow-
dered dye and 100 g solid NaCl to 40 to 50 mesh. Store in a
tightly stoppered bottle. Use 0.2 g of ground mixture for the titra-
tion in the same manner as murexide indicator. During titration
the color changes from red through purple to bluish purple to a
pure blue with no trace of reddish or purple tint. The pH of some
(not all) waters must be raised to 14 with 8 N NaOH until the
color persists.
c. Standard EDTA titrant, 0.01 M: Prepare standard EDTA titrant
and standardize against standard calcium solution as described
in Section 2340 C to obtain EDTA/CaCO3 equivalence. Standard
EDTA titrant, 0.0100 M, is equivalent to 1.000 mg CaCO3/1.00 mL;
use titrated equivalent for B in the calculations in 4.
3. Procedure
a. Pretreatment of water and wastewater samples: Follow the
procedure described in Section 3030 E or I if samples require
preliminary digestion.
b. Sample preparation: Because of the high pH used in this
procedure, titrate immediately after adding alkali and indicator.
Use 50.0 mL sample, or a smaller portion diluted to 50 mL so
the calcium content is about 5 to 10 mg. Analyze hard waters
with alkalinity higher than 300 mg/L CaCO3 by taking a smaller
portion and diluting to 50 mL. Alternatively, adjust sample pH
into the acid range (pH <6), boil for 1 min to dispel CO2, and cool
before beginning titration.
c. Titration: Add 2.0 mL NaOH solution or a volume sufficient
to produce a pH of 12 to 13. Stir. Add 0.1 to 0.2 g indicator mixture
Published Online: August 27, 2018
Revised: June 10, 2020
https://doi.org/10.2105/SMWW.2882.052
selected (or 1 to 2 drops if a solution is used). Add EDTA titrant
slowly, with continuous stirring to the proper endpoint. When using
murexide, check endpoint by adding 1 to 2 drops of titrant in excess
to make certain that no further color change occurs.
4. Calculation
A × B × 400.8
mg Ca/L =
mL sample
A × B × 1000
Calcium hardness as mg CaCO 3 /L =
mL sample
where:
A = mL titrant for sample and
B = mg CaCO3 equivalent to 1.00 mL EDTA titrant at the
­calcium indicator endpoint.
5. Precision and Bias
A synthetic sample containing 108 mg/L Ca, 82 mg/L Mg,
3.1 mg/L K, 19.9 mg/L Na, 241 mg/L CF−, 1.1 mg/L NO3−-N,
0.25 mg/L NO2−-N, 259 mg/L SO42−, and 42.5 mg/L total alkalinity
(contributed by NaHCO3) in distilled water was analyzed in 44
laboratories by the EDTA titrimetric method, with a relative stan-
dard deviation of 9.2% and a relative error of 1.9%.
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