Technetium thiocyanates

The chromatographic separation of technetium from molybdenum is based on the different extent to which molybdate and pertechnetate are adsorbed from alkaline and acid solutions. The distribution coefficient of molybdate between the anion exchanger Dowex 1-X8 and 3 M NaOH is 12, while it is 10 for pertechnetate under the same conditions. Molybdate is also adsorbed to a much lesser extent from hydrochloric acid solutions than pertechnetate. Thus, molybdemun can be eluted by hydroxide or HCl solutions while nitric acid, perchlorate or thiocyanate are used for the elution of technetium . 

Pertechnetate reduced in the presence of thiocyanate in an acid medium forms a red-violet thiocyanate complex with a maximum extinction at 513 nm. A yellow thiocyanate complex with a lower valence state of technetium is formed simultaneously . The red-violet complex [TcfNCS), ]" and the yellow complex... 

Technetium (VII) is adjusted to 3.5 to 4.0 M sulfuric acid solution. Hydrochloric, nitric and other volatile acids may be volatilized below 100 °C without loss of technetium (VII). The volume of the reduction medium is limited to 4.0 ml and that of cone, sulfuric acid to less than 1 ml to prevent possible phase separation of the final acetone solution. Then 4.0 M aqueous ammonium thiocyanate (0.5 ml) is added to the 3.5 to 4.0 M sulfuric acid solution of technetium (VII). 

This amount of thiocyanate is sufficient for both complete reduction and complex formation. Reduction is allowed to proceed for 30 to 45 s after the addition of the thiocyanate. A bright red color can readily be observed at a technetium (VII) concentration of 0.1 ng per ml. Acetone (6 ml) is then added and the volume of the solution mixed and adjusted to 10 ml with distilled water. At this point, the color has generally developed to less than 50% of its final intensity. Quartz 1-cm glass-stoppered cells are filled with the technetiiun solution and placed in a 20 °C water-cooled spectrophotometer. The extinction will approach a maximum intensity in 1 to 3 h. The maximiun extinction occurs at 510 nm with a molar extinction coefficient and standard deviation of 47,500 + 500 in 60 vol. % of the acetone-aqueous medium. An additional examination of the analysis may be carried out by extract-... 

Foster et al. have developed a method for determining technetium in dissolved nuclear fuel solutions. Tetrapropylammonium pertechnetate is doubly extracted from a basic medium into chloroform and the colored technetium (V) thiocyanate complex is formed in the chloroform phase by the addition of sulfuric acid, potassium thiocyanate and tetrapropylammonium hydroxide. The colored complex absorbs at 513 nm, has a molar extinction coefficient of 46,000 and is stable for several hours. Of more than 50 metals studied, none impairs measurements at ratios less than 100 to 1 mol with respect to technetium. Most anions do not disturb the determination of technetiiun. The standard deviation for a single determination is 0.09 fig over the range of 1 to 20 fig of technetium. 

The use of a special microtechnique has permitted the precipitation, weighing, and determination of about 2 /xg of technetium with a standard deviation of 0.08 /xg . The precipitate is filtered, washed with ice-cold water, dried at 110 °C and weighed as (CgH5) AsTcO. Permanganate, perchlorate, periodate, iodide, fluoride, bromide, thiocyanate anions and mercury, bismuth, lead, silver, tin and vanadyl cations as well as nitrate concentrations above 0.5 M interfere with the determination. 

Pertcchnetatc and Tc(lV) could be more sensitively analyzed in acidic media in the presence of thiocyanate by adsorption stripping voltammetry at the hanging mercury drop electrode using the differential pulse mode. Determinations down to 5-fO " g Te per ml were feasible. An intense eurrent signal at -1.32 V vs SCE was observed if only technetium and thiocyanate were present in the solution. Larger quantities of salts, e.g. chlorides and sulphates, decreased the sensitivity of the method considerably. This, however, could easily be avoided if, after electrodeposition was completed, the primary electrolyte was replaced by a pure solution of dilute acid for the stripping voltammetric step [100]. 

Potassium thiocyanate reduces pertechnetate in aqueous hydrochloric acid solution and forms thiocyanato complexes of technetium that arc extractable by a solution of 0.1 M 2-hexylpyridinc in benzene. Also Mo(VI), Au(IlI), As(III). Fe(III), Zn(II), and Hg(ll) are extracted under similar conditions, lire equilibrium is attained in about 3... 

---