206 Handbook of Water Analysis

combined with instrumental endpoint detection. Since reagent generating current can be controlled more
easily than volumetric reagent addition devices, many different, more or less titrators have been worked
out and investigated, starting from the early days of instrumental analysis [27].

8.2.3.2.2  Determination of Chloride with Mercurimetric Titration

The chloride ions form very strong, nondissociating complex with mercury(II) ions. The excess
of mercury ions after the equivalence point can be detected with an appropriate indicator.
Diphenylcarbazone is a good indicator that forms a blue-violet Hg(II)-diphenylcarbazone com-
plex. So, the chloride can be titrated with mercury(II) nitrate or mercury(II) perchlorate reagent.
According to Cheng [28], the analysis is easy and accurate in an 80% alcoholic solution at pH 3.5.
Bromide, iodide, sulfide, phosphate, chromate, and iron(III) interfere seriously with the mercuri-
metric titration. Fluoride, cyanide, and sulfate also should be eliminated before titration. Sulfate can
be precipitated with barium nitrate, while with the addition of thorium nitrate, both the phosphate
and fluoride can be precipitated and filtered off. The disturbing effect of sulfide and cyanide can be
eliminated by reacting with hydrogen peroxide or potassium permanganate. The mercurimetric titra-
tion works well with sample solutions containing more than 10 mg/dm 3 chloride. In the lower con-
centration range, the accuracy decreases but with a 1–2% error, 15 μg chloride could be determined
in a 20 cm 3 sample volume. The mercurimetric titration of chloride has been an effective officially
recommended method of water analysis [29,30].
Procedure: Two drops of bromophenol blue indicator solution (0.1% in ethanol) are added to the
aliquot of the sample solution containing 1–1.5 mg chloride. If the sample is basic (the indicator is
blue), it is titrated with 0.1 M HNO3 until yellow color appears. If it is acidic (yellow), 0.1 M sodium
hydroxide is added until color change. Then, 0.5 cm 3 0.1 M HNO3, and 100 cm3 95% ethanol (pH
should be about 3.6) and 0.5 cm3 diphenylcarbazone indicator solution (0.1% in ethanol) are added
to the titration vessel, and it is titrated with mercury(II) nitrate with intense agitation. Equivalence is
indicated by the appearance of the violet color. The indicator blank should be determined and taken
into consideration.

8.2.3.2.2.1  Reagents
Mercury(II) nitrate titrant (0.005 M):
Preparation: 3.4 g Hg(NO3)2·H2O is dissolved in about 600 cm3 nitric acid (0.01 M). It is kept
for 2 days in a closed container after being filtered and the volume made up to 2 dm3. The
solution needs to be standardized. For this, a mixture of 5 cm3 0.01 M sodium chloride and
10 cm3 distilled water is titrated as it is given previously.

8.2.3.2.3  Spectrophotometric Chloride Determinations

For the determination of the trace amount of chloride, different spectrophotometric methods have been
worked out. These are used in the analysis of highly purified waters, boiler feed waters, or other water
samples.

8.2.3.2.3.1  Determination with Mercury(II) Thiocyanate Reagent  Here, mercury(II) thiocyanate

reagent is added to the sample solution [31]. The chloride ions form sparingly dissociating mercuric
chloride complex and liberate a stoichiometrically equivalent amount of thiocyanate ions. The thio-
cyanate is reacted with iron(III) ions, giving intense red ferric thiocyanate complex according to the
following equations:

2Cl− + Hg(SCN)2 → HgCl2 + 2SCN−

SCN− + Fe3+ → Fe(SCN)2+

The absorbance is measured at 460 nm. The presence of bromide, iodide, cyanide, thiosulfate, sulfide,
thiocyanate, and nitrite ions, and the original color of the sample interfere with the determinations. The
method can be used in the range of 0.01–10 mg/dm3.

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