The kinetics and mechanism of decomposition of NTA complexes of FeIII, FeII, CoII, NiII, and CuII under hydrothermal conditions (425–573 K) have been examined. The relative rates at 573 K are CoIINTA− < NTA3−[Formula: see text] < NiIINTA− < FeIIINTA0 < H3NTA0 < CuIINTA− < H4NTA+. Aqueous CoIINTA− and FeIINTA−, like NTA3−, decomposed at 573 K by decarboxylation, precipitating Co(OH)2 and Fe3O4 respectively; NiIINTA− precipitated Ni(OH)2 initially but subsequently Ni metal. At 530 K, FeIIINTA0 solutions precipitated FeII3(NTA)2•H2O, but at higher temperatures Fe3O4 formed, the NTA ligand being reduced to HCHO and iminodiacetate (IDA) rather than decarboxylated. Similarly, CuIINTA−gave IDA and HCHO at temperatures as low as 425 K, forming first CuI (which precipitated as CuCl in the presence of Cl−) and then metallic Cu. The applicability of NTA to corrosion control in boilers and to 60Co removal from water-cooled nuclear reactors is briefly considered. The half-life of FeIIINTA in the hydrosphere is estimated at 80 years (cf. 8 × 106 years for free NTA), in the absence of photolysis or biodégradation.

Aqueous H3NTA, H2MIDA, H2IDA, and their anions decompose under hydrothermal conditions (400–580 K) according to first order kinetics by successive decarboxylations, oxidation by O2 being unimportant except at the highest temperatures. In the presence of added H+, the species H4NTA+ and, to a lesser extent, H3MIDA+ (but not H3IDA+), provide significant decomposition pathways through elimination of a —CH2COO— group (deacetylation). For HnNTA(3−n)−, first order rate coefficients kn for decomposition are k0 = 4.5 × 10−7, k1 ∼ 1 × 10−6, k2 ∼ 7 × 10−5, k3 = 2.1 × 10−4, and k4 = 1.0 × 10−2 s1, at 503 K and ionic strength 2.0 m, the spread in rates being due to differences in ΔS* rather than ΔH*. H2MIDA and H2IDA are comparable in reactivity to H3NTA, while their anions are much less reactive than the NTA species of the same charge. The good thermal stability of aqueous NTA commends it as a reagent for boiler servicing and for decontamination of water-cooled nuclear reactors. A potentiometric method for the estimation of mono-, di-, and tribasic aminoacids in aqueous mixtures of these is described.

The hydrothermal decomposition of iron(II) or iron(III) aminopolycarboxylate complexes can produce well-crystallized, stoichiometric Fe3O4. Best results were obtained when 0.1 m nitrilotriacetatoiron(III) was decomposed under N2 in 0.2–0.4 m NaOH at 497 K for 70 h or more.

Zersetzung von homogenen alkalischen Lösungen von Fe(II)‐ oder Fe(III)‐aminopolycarboxylat‐KOmplexen (Nitrilotri‐ (NTA), Methyliminodi‐, Iminodi‐, Ethylendinitrilotetraacetat) bei relativ niedrigen Drücken und Tempp.