Separation of uranium hexafluoride from plutonium hexafluoride by means of selective intercalation in graphite
BODY OF DISCLOSURE 
     It has been discovered and forms the basis of this disclosure that at partial pressures of less than 26 torr UF 6  will not intercalate into graphite. However, by virtue of its higher activity, PuF 6  can be expected to react with graphite at threshold partial pressures of less than 26 torr, i.e. a partial pressure at which UF 6  will not intercalate with graphite. 
     Consequently, based upon this discovery of a threshold pressure for UF 6  intercalation with graphite, a method is disclosed for the selective separation and sequestering of plutonium from uranium which comprises contacting uranium hexafluoride and plutonium hexafluoride with graphite at a UF 6  partial pressure of less than 26 torr whereby PuF 6  is selectively intercalated into the graphite while UF 6  remains unreacted, thereby effecting the desired separation. Preferably, the contacting of UF 6  and PuF 6  with graphite is conducted in the presence of excess fluorine. This is a consequence of the following thermodynamic relationship: considering the reaction 
     
         MF.sub.4 + F.sub.2 ⃡ MF.sub.6, 
    
     it shows at room temperature: 
     
         Kp(UF.sub.6) = [UF.sub.6 ]/[F.sub.2 ] = 10.sup.44 
    
     
         kp(PuF.sub.6) = [PuF.sub.6 ]/ [F.sub.2 ] = 4 × 10.sup.-5 
    
     in the graphite compound, both metals (M = Pu and U) will exist in the tetravalent state. This has been demonstrated by NMR and EPR for &#34;graphite/UF 6  &#34;. In view of the fact that pentavalent Pu is not a favorable oxidation state &#34;graphite/PuF 6  &#34; should contain tetravalent Pu. Any increase of fluorine pressure will, thermodynamically, force deintercalation of tetravalent uranium in graphite while leaving tetravalent plutonium untouched. In this manner, graphite becomes a &#34;sink&#34; and a container for the plutonium in the tetravalent oxidation state while rejecting thermodynamic intercalation with UF 6 . 
     Prior to the instant invention, the existence of a threshold UF 6  -graphite intercalation pressure was unknown. 
     Les Carbones, Vol. II, A. Herold, R. Setton, N. Platzer, eds, Masson et Cie, Paris, 1965 p. 563, references an article by J. Maire in the Proc. Second U.N. Intern. Conf. Peaceful Uses Atomic Energy, 28, and Geneva, 1958, pp 392-395; &#34;Fixation of Bromine and Uranium Hexafluoride on Carbons&#34;. 
     In this Paper, a series of tests were performed on spectroscopically pure material graphites and artificial graphites and medium graphitization. 
     One test involved introducing UF 6  at high pressure over carbon under vacuum at room temperature. At 300° C, UF 6  was irreversibly desorbed. 
     In another test, UF 6  was introduced at low pressure to graphite at saturation, natural graphite gained 175% of initial weight, artificial graphite gained 300% of initial weight. Basing weight gain as UF 6  adsorbed, these weights correspond to the formula C 16 .7 UF 6  and C 9 .77 UF 6  respectively. At 250° C, a reversible desorption of 80% of the material was performed in the artificial graphite specimen. 
     In yet another test, UF 6  was quickly brought into contact with graphite and it was not possible to desorb UF 6  at temperatures of to 300° C. 
     All of these experiments resulted in intercalation of UF 6  into graphite and would lead one to the inevitable conclusion that intercalation of UF 6  into graphite results at all conditions. 
     The instant separation method is based upon the discovery that at partial pressures below 26 torr UF 6  will not intercalate into graphite. Figure I is the graphite/UF 6  intercalation isotherm. From this it is clearly seen that a definite threshold partial pressure exists below which the amount of UF 6  which intercalates into graphite is negligible, approaching zero. The threshold pressure is about 26 torr. 
     By means of this discovery a separation process can be described for the separation of uranium from plutonium involving passing UF 6  and PuF 6  over graphite at a UF 6  partial pressure of less than 26 torr whereby because of the greater reactivity of PuF 6  it will intercalate into graphite while UF 6  will not intercalate because the contacting occurs at less than the threshold pressure. 
     Preferably, this contacting is performed in the presence of excess fluorine since such excess fluorine will participate in the de-intercalation of any UF 6  which may have sufficient energy to intercalate. 
     The process of the instant invention may be practiced using any type of graphite from any typical source. Normally graphite has a structure consisting of a hexagonal unit cell with dimensions A o  = (2.45 ± 0.10)A C o  = (6.7 ± 0.20)A. The only graphite which should be avoided is highly C axis oriented pseudo single crystal pyrolytic graphite. 
     Alternatively, the graphite may be pretreated with an oxidant which oxidizes the graphite and renders it resistant to UF 6  intercalation. Graphite reacted with CrO 3  /CH 3  CO 2  H and CF 3  CO 2  H/KMnO 4  (not in excess) results in the known intercalation compounds C 13  CrO 3  and C 30  CF 3  CO 2  H. UF 6  will not intercalate into these compounds at pressures at which it will intercalate into untreated graphite, i.e. partial pressures over 26 torr. Therefore, for situations requiring that graphite be in contact with UF 6  and remain unreacted with UF 6 , graphite pretreated with an intercalating oxidant should be used. In this manner, it is possible to produce a graphite material useful in electrochemical reactions and processes. Typical useful oxidants are selected from the group consisting of CuCl 2 , CuBr 2  AuCl 3 , AlCl 3 , GaCl 3 , InCl 3 , AlBr 3 , TiCl 3 , ZrCl 4 , HfCl 4 , SbCl 5 , TaCl 5 , FeCl 3 , CrCl 3 , CrO 2  Cl 2 , CrO 2  F 2 , MoCl 5 , α-WCl 6 , UCl 4 , UO 2  Cl 2 , UF 6 , ReCl 4 , CoCl 3 , RuCl 3 , RhCl 3 , PdCl 4 , PtCl 4 , IrCl 4 , ICl, ICl 3 , YCl 3 , SmCl 3 , CdCl 3 , YbCl 3 , DyCl 3 , EuCl 3 , HF, ClF 3 , BrF 3 , TiF 4 , IF 5 , AsF 5  , SbF 5 , NbF 5 , TaF 5 , XeF 6 , XeOF 4 , SbF 3  Cl 2 , HgCl 2 , MnCl 2 , NiCl 2 , ZnCl 2 , CdCl 2 , UCl 5 , NbCl 5 , MoOCl 4 , GaBr 3 , AuBr 3 , preferably CrO 3  and CF 3  CO 2  H.