In the Laboratory
Quantitative Analysis of Sulfate in Water by Indirect EDTA Titration
Deirdre Belle-Oudry
Department of Chemistry, University of Arizona, Tucson, AZ 85721; dbelle@email.arizona.edu
Measurement of common anions in water samples is typi-
cally carried out using the standard EPA method of ion chroma-
tography. However, for many teaching laboratories that are not
fortunate enough to be equipped with such instrumentation,
alternative wet chemical methods for quantifying anion content
are required. In addition to providing a low-cost alternative
technique for sulfate analysis, the experiment described herein
is an excellent tool to illustrate the notion that in some instances
simple wet chemical analyses are equally if not more valuable
than their instrumental counterparts.
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The titration of metal ions (e.g., Mg2+ and Ca2+) with
chelating agents such as EDTA is an important concept included
in many general chemistry laboratory curricula. Anionic species
can also be indirectly measured by EDTA titration. This type
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of titration involves precipitating the anion of interest with an
excess of a metal cation forming an insoluble salt, then back-
titrating the excess metal ions with EDTA. In this specific ex-
ample, excess BaCl2 is added to a water sample to precipitate the
sulfate ion as BaSO4. The excess Ba2+ is then back-titrated with
a standardized EDTA solution (1–3). The hardness of the water
sample must be accounted for as well. Students in our program
measure water hardness in their general chemistry lab. The inclu-
sion of this more advanced EDTA experiment in our upper-level
analytical lab course is an example of how one can integrate lab
activities and concepts at different levels in the curriculum. This
twist on the standard direct EDTA titration is most suitable for
a second- or third-year analytical chemistry laboratory course. It
can be used to introduce or to reinforce concepts such as chela-
tion, standardization, and water hardness, as well as to teach more
advanced concepts such as indirect and back-titrations.
Several different types of samples may be analyzed using
this method, including groundwater, soils (4), seawater (5, 6),
drinking water, and beverages (7). We opted to use “mock”
drinking water containing well-known amounts of sulfate,
calcium, and magnesium ions, since (i) a strong emphasis in
our analytical chemistry lab course is placed on the accuracy
of the students’ results, so it is important to know exactly what
amount is in the sample to assess their accuracy, (ii) we sought
an experiment of environmental relevance that would appeal to
students in a nonmajors course as well as to chemistry majors,
and (iii) it builds on students’ previous exposure to EDTA titra-
tions in general chemistry. The concentrations of sulfate and
metals in the mock water samples are within the range of 1–2
mM (~100–200 ppm SO42−). This is consistent with typical
sulfate levels in drinking water. While sulfate is not considered a
primary drinking water contaminant, it may affect the taste and
odor of water. The National Secondary Drinking Water Regula-
volumetrically into glass bottles. A few drops of concentrated
HCl are added to each bottle to create an acidic environment
conducive to the precipitation of BaSO4. An excess of 0.0100
M BaCl2 solution is then added to each bottle. The bottles are
covered with aluminum foil, boiled, and stirred for about an
hour while the student completes Part 2 of the experiment. The
bottles are removed from the hot plate and, once cool, capped
and set aside for two days until the next lab meeting. According
to Sijderius (1), the precipitation requires 24 hours to come to
completion. Therefore the experiment works best when carried
out over two lab periods.
In Part 2 of the experiment the student prepares and
standardizes a ~0.005 M EDTA solution in ultrapure water.
A standardized 0.0500 M ZnSO4 solution is first diluted 1:10;
this serves as their primary standard. Each student prepares an
indicator solution by dissolving a few mg of Eriochrome Black T
(EBT) in ~20 mL of ultrapure water. EBT was chosen as the
indicator for this experiment since it gives a clear end point
when used with the metal ions of interest (Ba2+, Ca2+, and Mg2+)
(9). The pH of the solution is first adjusted to a suitable range
(~9.5–10) by adding pH 10 buffer solution. This step is crucial,
as the EBT indicator transition is best observed in this range
(9). A few drops of indicator are added to the EDTA just before
titration with the standard ZnSO4 solution. The end point is
observed when the solution turns from pink to pure blue. Note
that this is a gradual change, and the solution first turns purple
before turning blue.
The hardness of the water sample is measured in Part 3.
Salts containing Mg2+ and Ca2+ were added to mimic a real
water sample and demonstrate that these interfering ions must
be accounted for in back-titration of the Ba2+. A portion of the
water sample is added to an Erlenmeyer flask and the pH is ad-
justed with pH 10 buffer solution. The solution is then titrated
with the standardized EDTA solution. The solution turns from
blue to fuchsia at the end point.
Finally, in Part 4, the excess, unprecipitated Ba2+ is found by
titrating the samples from Part 1 with the standardized EDTA
solution. The procedure is nearly identical to that in Part 3, with
a bit more pH 10 buffer added to counteract the effect of the
acid added in Part 1. Note that it is not necessary to filter the
BaSO4 precipitate before this final titration. By measuring the
total amount of metal in the solution of the precipitated samples
and subtracting out the amount of metal due to water hardness
measured in Part 3, the amount of excess Ba2+ is found. The
concentration of SO42− in the sample can easily be calculated:
total amount amount
added Ba2
  
excess Ba2
tions therefore recommend that the maximum level of sulfate in
drinking water be limited to < 250 ppm (8). SO 4 2  
VSO 2
4

Experimental Overview
The experiment consists of four parts and is carried out
during two 3-hour lab periods. In Part 1, the mock water
sample (prepared in advance by the teaching staff ) is pipetted
Hazards
Barium chloride is toxic and can irritate the skin, eyes, and
respiratory system (10). Having a solution prepared in advance

© Division of Chemical Education  •  www.JCE.DivCHED.org  •  Vol. 85  No. 9  September 2008  •  Journal of Chemical Education 1269
 In the Laboratory
Table 1. Typical Student Results from EDTA Experiment
Sulfate Concentration/
Hardness/(mmol L–1)
Student
mM
Measured True Measured True
A 2.06 ± 0.02 2.00 1.19 ± 0.02 1.20
B 2.05 ± 0.01 2.00 1.37 ± 0.01 1.40
C 2.06 ± 0.01 2.00 1.23 ± 0.01 1.20
D 2.13 ± 0.03 2.00 1.23 ± 0.03 1.20
E 1.99 ± 0.02 2.00 1.48 ± 0.02 1.40
Note: Uncertainties were calculated at the 95% confidence level.
helps to minimize inhalation risk. However, students should
avoid getting this solution on their skin. Concentrated hydro-
chloric acid and the pH 10 ammonium buffer are corrosive and
may cause burns. Zinc sulfate is environmentally harmful. All
chemicals from this experiment should be considered harmful
and disposed of as hazardous waste.
Results and Discussion
Typical results from this experiment are fairly accurate.
For a recent class of 24 students, the average percent error was
about 2.56% for sulfate and 3.43% for hardness. The method
also proved fairly precise, with typical percent relative standard
deviations of less than 1.5%. Table 1 shows representative results
obtained by five students in the class. For each student, the re-
sults shown represent an average of 3–5 trials.
Comparisons with other methods for sulfate determina-
tion, such as ion chromatography and gravimetric analysis of
BaSO4 precipitate, are useful for illustrating the advantages
and disadvantages of each method. Gravimetric analysis (EPA
Method 375.3) is comparable in accuracy (1.9% error) but
is typically not as precise (4.7% RSD) as this EDTA method
(11). Recent measurements in our laboratory of these same
water samples using a Dionex DX-300 ion chromatograph (IC)
showed IC to be more accurate (< 1% error). However, the IC
analysis was much more time consuming, requiring 7 hours of
lab time to obtain enough data for a statistically meaningful re-
sult. Additionally, neither gravimetry nor IC provides the water
hardness information that this EDTA titration gives. Overall,
the experiment described herein achieves the objective of pro-
viding a fast, precise, and fairly accurate method that teaches
students a number of important analytical concepts.
This experiment can be implemented in any quantitative
analysis course or even in an honors general chemistry course. It
is best done over the course of two lab periods, since the BaSO4
precipitation takes about 24 hours to complete (1). Students
can usually complete the first three parts of the experiment
within one three-hour lab period and finish the final titration
of the excess Ba2+ during the second period. To shorten the
time required, one could prepare a standardized EDTA solu-
tion in advance. Another experimental variation would be to
substitute the measurement of the water hardness with removal
of the interfering cations by passing the sample through a cat-
1270 Journal of Chemical Education  •  Vol. 85  No. 9  September 2008  •  www.JCE.DivCHED.org  •  © Division of Chemical Education
ion exchange resin (12) before precipitation. One could also
complex the metal ions with masking agents before titration
with EDTA. Real drinking water samples could be substituted
for the lab-prepared sample for courses in which accuracy is
not as crucial.
Conclusions
The indirect titration of sulfate is a valuable exercise for
teaching a number of important concepts to students in the ana-
lytical chemistry lab, from the utility of wet chemical techniques
to water quality. It requires inexpensive and common chemicals
and equipment. The procedure can be varied in several ways to
fit the goals of a particular course and student skill levels.
Literature Cited
1. Sijderius, R. Analytica Chimica Acta 1954, 11, 28–32.
2. Munger, J. R.; Nippler, R. W.; Ingols, R. S. Anal. Chem. 1950, 22,
1455.
3. Kowalczyk, G. S.; Simpson, C. P. An Indirect Determination of
Sulfate by Back-Titration of Barium with EDTA. In Abstracts,
37th Middle Atlantic Regional Meeting of the American Chemical
Society; American Chemical Society: Washington, DC, 2005.
4. Purokoski, P.; Lakanen, E. Acta Agr. Scand. 1959, 9, 355–360.
5. Howarth, R. W. Limnol. Oceanogr. 1978, 23, 1066–1069.
6. Page, J. O.; Spurlock, W. W. Analytica Chimica Acta 1965, 32 (6),
593–595.
7. Krasnova, N. S.; Gamarnik, B. A. Zhurnal Analiticheskoi Khimii
1989, 44 (5), 948–950.
8. U.S. EPA Drinking Water Contaminants. http://www.epa.gov/
safewater/mcl.html#inorganic (accessed May 2008).
9. Ueno, K. J. Chem. Educ. 1965, 42, 432–433.
10. Sigma-Aldrich Home Page. http://www.sigmaaldrich.com (ac-
cessed May 2008).
11. Sulfate by Gravimetric Determination (Method 375.3). In
Methods for the Analysis of Water and Wastes (MCAWW),
EPA/600/4-79/020; U. S. E. P. A. Office of Research and Devel-
opment: Washington, DC, 1983.
12. MacKellar, W. J.; Wiederanders, R. S.; Tallman, D. E. Anal. Chem.
1978, 50 (1), 160–163.
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Supplement
Student handouts
Instructor notes including answers to the questions in the student
handout
JCE Featured Molecules for September 2008 (see p 1296 for details)
Structures of EDTA and Eriochrome Black  T discussed in this
article are available in fully manipulable Jmol format in the JCE
Digital Library at http://www.JCE.DivCHED.org/JCEWWW/
Features/MonthlyMolecules/2008/Sep/.