The method used by the author for the estimation of free chlorine is as
follows: place 500 c.cms. of the sample in a stoppered bottle, add 1
c.cm. of 5 per cent KI solution, 2 drops of conc. HCl and 1 c.cm. of
starch solution and titrate with N/1000 sodium thiosulphate until
colourless. The difficulty introduced by the opalescence of the liquid
is overcome by pouring portions of the liquid into two Nessler tubes and
adding a drop of thiosulphate solution to one and noting if any
reduction of colour occurs on shaking; if the intensity of the colour is
diminished, the contents of both tubes are poured back into the bottle
and titrated until no further colour removal, as shown by the tubes, can
be obtained. One c.cm. of N/1000 sodium thiosulphate = 0.07 p.p.m. of
available chlorine when 500 c.cms. of water are used.
Adams[4] has employed the colorimetric method of estimating the colour
obtained after the addition of dilute H_{2}SO_{4}, KI, and starch but
used standard solutions of dyes for comparison. The standards were
prepared from mixtures of Brilliant Mill Green "S" and Cardinal Red "J"
and were made up weekly.
Phelps found that ortho-tolidine in acetic acid solution produced an
intense yellow colouration with free chlorine and suggested the use of
this reagent as a qualitative test for chlorine. Ellms and Hauser[5]
developed this process into a quantitative one and substituted
hydrochloric acid for acetic acid as a solvent. One c.cm. of the reagent
(1 gram of pure _o_-tolidine dissolved in 1 litre of 10 per cent of
hydrochloric acid) is added to 100 c.cms. of the sample in a Nessler
tube and the colour compared after five minutes with permanent standards
made up with mixtures of potassium bichromate and copper sulphate. This
method was adopted as the official standard method of the American
Public Health Association; the details are given in the Appendix (p.
147).
The author has found that this method gives excellent results except for
coloured waters. The colouring matter in many waters diminishes in
intensity on the addition of acids and is somewhat similar in tint to
that produced by addition of _o_-tolidine. If the reaction is used
qualitatively on coloured treated water and a comparison made with the
untreated sample, a negative result, due to the reduction in colour
produced by the acid being greater than the increase caused by the
reagent, might be obtained when traces of free chlorine are present.
Similar difficulties are encountered when quantitative comparisons are
made against permanent standards.
Benzidine (Wallis[6]) has also been suggested for the detection of free
chlorine. On adding this reagent a blue colouration is produced but on
stirring it rapidly changes to a bright yellow which is proportional in
intensity to the amount of free chlorine present. Ellms and Hauser[5]
investigated benzidine in 1913 and found it to be inferior to
_o_-tolidine as a test reagent for free chlorine.
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