I Oxide in Carbon Tetrachloride Solution

A solution of chlorine (I) oxide in carbon tetrachloride is easier to obtain and safer to handle than the pure compound. The first3 of the two procedures given is better for laboratory syntheses the second resembles an industrial method of producing chlorine(I) oxide.4 On a large scale, the second is the more economical and avoids the use of toxic mercury compounds. As a laboratory procedure, it has the disadvantages of being difficult to control and of converting only about half of the chlorine dissolved in the carbon tetrachloride into chlorine(I) oxide. 

A dry 1-1. three-necked flask is equipped with a sealed stirrer, an inlet tube extending nearly to the bottom of the flask, and an exit tube leading to a hood. Four hundred fifty milliliters of dry carbon tetrachloride is placed in the flask and cooled with an ice bath. The stirrer is started, and chlorine is passed into the liquid. From time to time, a 1-ml. sample of the resulting solution is titrated iodometrically to determine its chlorine content. When a concentration of at least 50 g. of chlorine per liter is reached, the flow of chlorine is stopped. The flask is warmed to 25°, and at least 3.36 g. of dry yellow mercury(II) oxide per gram of chlorine (1.1 mol/mol of chlorine) is added. Stirring is continued for 45 minutes, after which interval 

Mercury(II) oxide is recovered as outlined above. The same precautions regarding contact with the skin should be observed. 

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Sodium chlorate, formation of, in preparation of chlorine (I) oxide in carbon tetrachloride solution, 5 159n. 

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