Oxalate complex ions, precipitation

After preparing a homogeneous solution of the precursors, powder precipitation is accompHshed through the addition of at least one complexing ion. For PLZT, frequently OH in the form of ammonium hydroxide is added as the complexing anion, which results in the formation of an amorphous, insoluble PLZT-hydroxide. Other complexing species that are commonly used are carbonate and oxalate anions. CO2 gas is used to form carbonates. Irrespective of the complexing anion, the precipitated powders are eventually converted to the desired crystalline oxide phase by low temperature heat treatment. 

When ammonium oxalate or potassium oxalate is slowly added to a solution containing actinides, actinide(IV) and (VI) ions form soluble complex ions, whereas actinide(III) ions precipitate as oxalates. Actinide(IV) and (VI) ions present in ammonium or potassium oxalate solutions precipitate by addition of cobalt (III) or chromium(III) complex salts. 

IV) oxalato complex ions with hexaureachromium(III) chloride. The concentrations of Th(IV) or Pu(IV) ions in the supernatant depend greatly on the concentration of hexaureachromium(III) chloride and decrease rapidly with increasing concentrations of hexaureachromium(III) chloride. On the other hand,concentrations of ammonium oxalate in the range of 0.04 to 0.1M have little effect on this precipitation reaction. Although the precipitation behavior of Pu(IV) ion is similar to that of Th(IV) ion,the concentration of Pu(IV) ions in the supernatant is always over 100 times higher than that of Th(IV) ions. 

Hexamminecobalt(III) salt cannot be used as a precipitant in the oxalato complex precipitation system because it precipitates as hexamminecobalt(III) oxalate. Besides the hexaureachro-mium(III) salt, hexamminechromium(III), tris(ethylenediamine)cobalt (III) or tris(trimethylenediamine)cobalt(III) salts can be used as precipitants. Hexamminechromium(III) and tris(ethylenediamine) cobalt (III) salts form precipitates with actinide(IV) or (VI) oxalato complex ions, whereas tris(trimethylenediamine)co-balt(III) salt forms precipitates with Th(IV) or U(VI) oxalato complex ions leaving Pu(IV) ion in the supernatant solution.Therefore, this reagent plays the role of both a separating agent and a precipitant and is applicable for the separation of Pu(IV) ion from Th(IV) or U(VI) ion. 

The oxalate system is not useful for the separation of Cm-(III) ion from Am(VI) ion because Am(VI) ion is reduced by oxalate ion and its oxalato complex precipitate like that of U(VI) ion with cobalt(III) complex ion cannot be obtained. 

No precipitation of tin(IV) sulphide occurs in the presence of oxalic acid, due to the formation of the stable complex ion of the type [Sn(C204)4(H20)2]4 this forms the basis of a method of separation of antimony and tin. 

Sulfate, oxalate, and tartrate form complex ions with pentavalent vanadium in aqueous solution. Oxalate complexes are stable to the point that only in the presence of excess oxalate does a precipitate form upon addition of solutions containing calcium salts. 

In the processing of nuclear materials, precipitation/coprecipitation techniques are used for the separation of the actinides from most fission products. Both fluoride and oxalate complexes of these metal ions are sufficiently insoluble to accomplish this separation (Stary 1966). Coprecipitation with bismuth phosphate has also been used for this purpose (Stary 1966). Because of their insensitivity to subtle changes induced by minor cation-radius changes, such techniques are not useful for the separation of the lanthanides from the trivalent actinide metal ions. 

Predict whether cadmium oxalate, CdC204, will precipitate from a solution that is 0.0020 M Cd(N03)2, 0.010 M Na2C204, and 0.10 M NH3. Note that cadmium ion forms the Cd(NH3)4 complex ion. 

The most selective precipitating reagent for the rare earths is oxalic acid. In the presence of an excess of the oxalate ion, however. Sc forms a soluble oxalate complex and the heavy lanthanides are not completely precipitated. 

The left-hand maximum A is due to the fact that the solution is so acid that oxalate ions exist primarily as undissociated oxalic acid and the weak tin-oxalate complex decomposes, while the right-hand maximum C arises from the fact that the S and OH" ion concentrations are increasing enough, to precipitate tin sulfide and hydroxide despite the existence of the tin-oxalate complex in solution. And finally, at high pH s, formation of thiostannate ions once again inhibits precipitation of SnS. ... 

One physiological inhibitor of clotting is heparin, w hich is formed in mast cells. Heparin acts at different steps in the complicated process First, it inhibits the formation of plasma thrombokinase second, the activation of prothrombin third, the enzymic activity of thrombin. Many animal poisons (e.g. the blood poison, hirudin, extracted from leeches) also inhibit blood clotting. In vitro, clotting is prevented commonly by binding Ca++ ions (precipitation with fluoride or oxalate complex formation with citrate, etc.). 

Several carboxylates, both simple salts and complex anions, have been prepared often as a means of precipitating the An ion from solution or, as in the case of simple oxalates, in order to prepare the dioxides by thermal decomposition. In K4[Th(C204)4].4Fl20 the anion is known to have a 10-coordinate, bicapped square antipris-matic structure (Fig. 31.8b). -diketonates are precipitated from aqueous solutions of An and the ligand by addition of alkali, and nearly all are sublimable under vacuum. [An(acac)4], (An = Th, U, Np, Pu) are apparently dimorphic but both structures are based on an 8-coordinate, distorted square antiprism. 

Calcium can be determined as the oxalate by precipitation from homogeneous solution by cation release from the EDTA complex in the presence of oxalate ion.28... 

If the metallisable dye is insoluble in water, a miscible solvent such as ethanol or ethylene glycol may be added. Polar solvents such as formamide or molten urea have sometimes been preferred. It is likely that such solvents will preferentially displace water molecules and coordinate with the chromium (III) ion as the first step in the reaction. If colourless organic chelates of chromium, such as those derived from oxalic or tartaric acid, are used instead of or in addition to hydrated chromium (III) salts, the difficulty of replacing the strongly coordinated water molecules in the first stage of the reaction is eliminated. In this way the initial reaction can be carried out at high pH without contamination by the precipitation of chromium hydroxide. Use of the complex ammonium chromisalicylate (5.12) in this connection should also be noted (section 5.4-1). 

Another lanthanide carboxylate complex that also contains nonacoordinated lanthanide ion in a monocapped square antiprismatic arrangement of nine oxygens is the erbium oxalate trihydrate with the composition Er(OOCCOO) (HOOCCOO) (OH2)3. This complex crystaUizes (767) in space group P4/ with 0 = 8.664, c =6.4209 A and Z=2, when the precipitate of erbium oxalate, ob-... 

Coprecipitation of the metals is usually achieved from an aqueous solution of nitrates upon addition of anions such as carbonates, citrates, or oxalates (10)(24-27). First reports in this field have underlined the necessity to neutralize the pH of the solution in order to obtain complete precipitation of barium or strontium. Also, oxalate or citrate ligands may bind to two different cations. This should allow a better mixing at a microscopic level. However, care should be taken since some cations such as Y or La may precipitate as double salt complexes with alkaline ions that have been added to the solution as hydroxides in order to control the pH (24). 

A widely applicable masking agent is sodium triphosphate, Na5P3Oi0-6H2O, which readily complexes with a very wide variety of cations in all groups of the Periodic Table, preventing their precipitation by alkali hydroxide, ammonia, phosphate, carbonate or borate. It is used commercially as Calgon to mask calcium which cannot then form precipitates with citrate, fluoride or oxalate ions and in many other instances (see Table 3). 

The tram salt may be distinguished from the cis complex because it forms precipitates in aqueous solutions with chromate, oxalate, or thiosulfate ions the out salt reacts negatively under these conditions. 

Principle of Separation. Uranium as the U02+ ion in strong chloride solutions forms an anionic chloride species such as U02C13 thorium does not. If a solution in which the chloride ion has been adjusted to form the uranyl chloride complex is passed through a cation exchange column, the uranium passes through the column and cationic Th+4 is absorbed. After the column is washed to insure that no uranium remains, the absorbed thorium is complexed with oxalate ions to form an anion and is released from the column. Although thorium generally is precipitated with oxalate ions, with excess quantities of oxalate it forms a soluble anionic species. The mass of thorium in this experiment is extremely low relative to that of oxalate and will not form a precipitate. 

Of special interest was the removal of lead. Most lead was removed during the loading and first washing cycle, which indicates lead is being complexed by the chloride ion. This complex is currently being used to aid in the decontamination of lead in the oxalate precipitation process. 

As the result of oxalate ion complexing of Al3+, precipitation of Am-Cm-A1(N03)3 solutions was not straightforward. Using Dy as a stand-in for Am-Cm, simulated solutions were prepared where the ratio of A1(N03>3 to Dy (1 03)3, KF, NaN03, and Hg(1 03)2 was held constant as would result in actual process solutions. However, the total ratio of these species to free nitric acid was varied in the stock solutions. Precipitation conditions were simulated by additions of either a half-equal or an equal volume of either an 0.9M or a saturated ( 2M) potassium oxalate... 

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