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.