RI 5047 Iodometric Determination Of Selenium In Ores And Flue Dusts ? Introduction And Summary

[In the original Norris and Fay method for determining selenium, selenious acid is reduced by an excess of standard thicsulfate in accordance with the following reaction: H2Se03 + 4Na2S203 + 4HC1 = Na2SeS406 + Na2S406 + 4NaC1 + X20. (1) The excess thiosutfate is then back-titrated with standard iodine solution. The disadvantages of ouch a method are obvious. On an unknown sample, the quantity of thiosutfate required would be difficult to determine; a definite excess is required, but large back titrations would be undesirable. Inasmuch as thiosulfate is decomposed by acid, considerable error may be introduced in this method, the amount depending on the acidity, temperature, concentration of excess thiosulfate, duration of contact between thiosulfate and acid, and other factors, In a critical study of the Norris and Fay method, Coleman and McCrosky3/ show that the method is accurate to less than .1 part per thousand if the excess of this sulfate Is not greater than 5 ml. of 0.1 N solution (in 1.0 ml. of 0.x4 N sulfuric acid) whether the titration is made at 0° or 20°C. A greater excess produced unsatisfactory values at either temperature. Coleman and McCrosky regulated the excess thiosulfate by adding 5-ml. portions of thiosulfate solution followed by the addition of 1 to 3 drops of 2.5 percent potassium iodide in the presence of starch. If a starch-iodine blue color formed locally around the drops of potassium Iodide, the reduction of selenious acid was not complete. On stirring the solution, the local blue color fades and another 5-ml. portion of thiosulfate is added. When addition of potassium iodide fails to produce a local blue color, reduction of selenious acid is complete, and the excess thiosulfate is then back-titrated with standard Iodine solution. The number of equivalents involved in the reduction of selenious acid by either thiosulfate or iodide is the same, and therefore no correction need be made for the potassium iodide. This procedure is much better than the original Norris-Fay titration, but acidity and time would stilt be rather critical factors subject to variation with individual technique. Also, the method still requires the lose of two standard solutions, a rather undesirable factor from the standpoint of routine application.]