Assays by oxygen flask combustion

-Developed by Schoniger(1955). -Rapid assay method for organically combined halogens. -Halogen is released following the complete combustion of organic matter by oxygen. -Halogen is absorbed by caustic soda solution.

-In case of iodo-compound, a mixture of iodine & iodate are formed. -Oxidation is carried out with bromine. -After acidification in the presence of iodide, six fold yield of iodine is generated. -The iodine is titrated against sodium thiosulphate.

-The method is useful for expensive materials & product in which the halogen-containing material is present at low dosage.

-The method is adapted to determine elemental sulphur. -Sulphur is oxidised to sulphur trioxide absorbed in water. -To ensure the complete oxidation, hydrogen peroxide is also added in the water. -Then sulphur is determined by titrating with barium perchlorate solution using indicator alizarin red S or thoron/methylene blue as appropriate.

- The method is applicable in the determination organo-mercury compounds as well.

Apparatus:
i)Iodine flask(500ml) as per British standard specification (BS 2735:1956). ii)To the stopper platinum wire is fused. iii)To the wire a platinum gauze of specified dimension is attached. iv)The gauze complies to dimension of No.36 sieve.

Propyliodone: Determination of the percentage of C10H11I2NO3

C10H11I2NO3 3I2 + 6NaOH 5NaIO3+ 3H2O 5[NaI+3Br2 +3H2O NaIO3 +6HBr] 6[NaIO3 +5KI +6HBr 3I2 +NaBr+5KBr] I2+ 2Na2S2O3 2NaI +Na2S4O6 3X447g C10H11I2NO3 6I NaIO3 36I 36000ml M 0.7450mg C10H11I2NO3 1ml 0.02M Na2S4O6

-Accurately weighed sample is folded in an ashlesfilter paper. -The folded paper is placed in the platinum gauze cup. -A narrow strip of filter paper is inserted in the folded paper to act as a fuse. -Air is displaced from the flask with oxygen & the neck is moisten with water. -The flask is swirled to saturate the solution with O2

-Water & M sodium hydroxide are placed in the flask & was filled with oxygen . -End of the fuse is lit & the stopper is inserted immediately. -The flask is held firmly in place. -The flask is tilted in order to prevent incompletely burned material from falling into the liquid. -Upon completion of the combustion, the flask is shaken vigorously for 5 minutes.

-Few ml of water is placed in the cap, the stopper is carefully withdrawn. -The stopper & wire assembly are washed with water & excess of acetic bromine solution is added.
-Then the solution is allow to stand for two minutes.

-Iodide is oxidised to iodate by bromine in potassium acetate-acetic acid buffer solution.

-Excess bromine(reduction to HBr) is removed by addition of formic acid. -Potassium iodide is added & titrated with sodium thiosulpahte(V.S.) using starch mucilage as indicator.

Cognate determination: Iophendylate injection, Liothyronine sodium Propyliodone suspension, Proppyliodone oily suspension, Thyroxine sodium, Nitroxynil

Fluocinolone acetonide: -Borosilicate glass must be avoided as fluorine reacts with boron present in the hard glass.

-Organically combined fluorine is converted to fluorine by combustion in oxygen in a silica or soda glass flask.
-Absorbed fluorine in water is determined colourimetrically at 610nm using alizarin fluorine blue & cerous nitrate in an acetate buffer. -Standard used is sodium fluoride.

Other uses of oxygen flask method: -Determination of fluorine in cloxacillin sodium to supplement the assay. -To establish the presence of chlorine in diloxanide furoate & chlorthalidone.

Reference:
IP2007. A.H. Beckett/J.B.Stenlake Practical pharmaceutical chemistry.