The iron(III)-catalyzed oxidation of EDTA in aqueous solution

1980 ◽  
Vol 58 (19) ◽  
pp. 1999-2005 ◽  
Author(s):  
Ramunas J. Motekaitis ◽  
Arthur E. Martell ◽  
David Hayes ◽  
Wayne W. Frenier
Keyword(s):  
Aqueous Solution ◽  
Elevated Temperatures ◽  
Iminodiacetic Acid ◽  
Nitrilotriacetic Acid ◽  
Similar Reaction ◽  
Reactive Intermediate ◽  
Reaction Products ◽  
Reaction Proceeds ◽  
Catalyzed Oxidation ◽  
By Products

At temperatures above 100 °C iron(III) oxidizes coordinated EDTA to ethylenediaminetriacetic acid in aqueous solution in the absence of molecular oxygen. The reaction proceeds with an activation energy of 28.6 kcal/mol, and its rate is directly proportional to the concentration of Fe(III) and inversely proportional to pH. At 125 °C, the halflife of Fe(III) in the presence of excess EDTA is about 3 h at pH 9.3, but increases to >70 h at pH 5.4. The reaction is stoichiometric and no other reaction products or by-products were detected by nmr, gc, and gc – mass spectroscopy. In the presence of oxygen iron catalyzes quantitative oxidation of ethylenediamine-N,N,N′,N′-tetraacetic acid (EDTA) to ethylenediaminetriacetic acid. The copper(II)–EDTA chelate undergoes a similar reaction but higher temperatures [Formula: see text] are required. Iron(III) also oxidizes nitrilotriacetic acid (NTA) to iminodiacetic acid (IDA) and glycine. The hydrolyzed species Fe(OH)EDTA is shown to be the reactive intermediate, and the well-known (Fe–EDTA)2O4− μ-oxo dimer is shown not to exist at elevated temperatures (above 100 °C). Probable mechanisms are proposed for these reactions and comparisons are made with earlier work.

Thermal degradation of EDTA chelates in aqueous solution

1982 ◽  
Vol 60 (10) ◽  
pp. 1207-1213 ◽  
Author(s):  
Ramunas J. Motekaitis ◽  
X. B. Cox III ◽  
Patrick Taylor ◽  
Arthur E. Martell ◽  
Brad Miles ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Thermal Degradation ◽  
Elevated Temperatures ◽  
Degradation Products ◽  
Iminodiacetic Acid ◽  
Reaction Products ◽  
Degradation Rates ◽  
Lower Temperature Range ◽  
Higher Temperature ◽  
Lower Temperature

The thermal degradation of Ca(II), Mg(II), Zn(II), Fe(II), and Ni(II) chelates of EDTA was investigated in alkaline aqueous solution at elevated temperatures (230–310 °C). The kinetics of decomposition were followed by nmr, titrimetry, and spectrophotometry. Reaction products were identified through nmr and by gas chromatography. The relative order of degradation rates, as measured by the loss of EDTA, was found to be Mg(II) > Ca(II) > Zn(II) > Fe(II) > Ni(II). The main degradation products formed in the lower temperature range (~250 °C) are iminodiacetic acid, hydroxyethyliminodiacetic acid, and ethylene glycol. Higher temperature products are primarily dimethylamine and carbon dioxide. The rates of degradation of Ca(II), Mg(II), and Zn(II) EDTA chelates are considerably enhanced when either phosphate is present or a glass-lined autoclave is employed.

Hydrolysis and ammonolysis of EDTA in aqueous solution

1979 ◽  
Vol 57 (9) ◽  
pp. 1018-1024 ◽  
Author(s):  
Ramunas J. Motekaitis ◽  
David Hayes ◽  
Arthur E. Martell ◽  
Wayne W. Frenier
Keyword(s):  
Aqueous Solution ◽  
Iminodiacetic Acid ◽  
Order Rate Constant ◽  
Spectroscopic Techniques ◽  
Reaction Products ◽  
First Order ◽  
Molar Ratios ◽  
Ph Values ◽  
Rate Of Hydrolysis ◽  
Protonated Nitrogen Atom

The hydrolysis and ammonolysis of EDTA were studied in aqueous solution over a range of temperatures and at various pH values with the aid of nmr, gc, and gc – mass spectroscopic techniques. At high pH in the presence of ammonia, both ammonolysis and hydrolysis occur with the production of N-(2-aminoethyl)iminodiacetic acid (UEDDA), N-(2-hydroxyethyl)-iminodiacetic acid (HEIDA), and iminodiacetic acid (IDA) in molar ratios such that [IDA] = [UEDDA] + [HEIDA]. The first-order rate constant for the disappearance of EDTA at 175 °C in dilute aqueous ammonia is 8.6 × 10−5 s−1 whereas in the absence of ammonia its hydrolysis constant is 4.2 × 10−5 s−1. The value of ΔH0 for this reaction is approximately 35 kcal/mol. When methylamine replaces ammonia, the UEDDA is replaced by N-(2-methylaminoethyl)iminodiacetic acid. The rate of hydrolysis is increased by the presence of a tertiary amine but the latter does not become incorporated into the reaction products. A reaction mechanism is proposed involving bimolecular SN2 attack by base on a carbon atom of the ethylene bridge adjacent to a protonated nitrogen atom of EDTA with concomitant displacement of iminodiacetic acid.

scholarly journals Hybrid Cements. Mechanical Properties, Microstructure and Radiological Behavior

Molecules ◽  
2022 ◽  
Vol 27 (2) ◽  
pp. 498
Author(s):  
Ana María Moreno de los Moreno de los Reyes ◽  
José Antonio Suárez-Navarro ◽  
María del Mar Alonso ◽  
Catalina Gascó ◽  
Isabel Sobrados ◽  
...  
Keyword(s):  
Spectrometric Method ◽  
Similar Reaction ◽  
Reaction Products ◽  
Curing Conditions ◽  
Naturally Occurring ◽  
Powder Samples ◽  
Alkaline Activator ◽  
Industry Sustainability ◽  
By Products ◽  
Alkali Activated

The use of more eco-efficient cements in concretes is one of the keys to ensuring construction industry sustainability. Such eco-efficient binders often contain large but variable proportions of industrial waste or by-products in their composition, many of which may be naturally occurring radioactive materials (NORMs). This study explored the application of a new gamma spectrometric method for measuring radionuclide activity in hybrid alkali-activated cements from solid 5 cm cubic specimens rather than powder samples. The research involved assessing the effect of significant variables such as the nature of the alkaline activator, reaction time and curing conditions to relate the microstructures identified to the radiological behavior observed. The findings showed that varying the inputs generated pastes with similar reaction products (C-S-H, C-A-S-H and (N,C)-A-S-H) but different microstructures. The new gamma spectrometric method for measuring radioactivity in solid 5 cm cubic specimens in alkaline pastes was found to be valid. The variables involved in hybrid cement activation were shown to have no impact on specimen radioactive content. The powder samples, however, emanated 222Rn (a descendent of 226Ra), possibly due to the deformation taking place in fly ash structure during alkaline activation. Further research would be required to explain that finding.

Ag (I) Catalyzed Oxidation of SO2 in Aqueous Solution Differing Effect of Benzoate Ions in Acidic Medium

2017 ◽  
Vol 7 (4) ◽  
Author(s):  
Arun Kumar Sharma ◽  
Pradeep Parasher ◽  
Rashmi Sharma ◽  
Davarakonda S.N. Prasad
Keyword(s):  
Aqueous Solution ◽  
Acidic Medium ◽  
Differing Effect ◽  
Catalyzed Oxidation

Pattern Formation in the Methylene Blue-Fructose-Oxygen System in Aqueous Solution and in Gel Systems

2000 ◽  
Vol 65 (9) ◽  
pp. 1394-1402 ◽  
Author(s):  
Ľubica Adamčíková ◽  
Mária Hupková ◽  
Peter Ševčík
Keyword(s):  
Aqueous Solution ◽  
Methylene Blue ◽  
Pattern Formation ◽  
Alkaline Ph ◽  
Initial Reactant ◽  
Nonlinear Reaction ◽  
Oxygen System ◽  
Hydrodynamic Processes ◽  
Liquid Layer Thickness ◽  
Catalyzed Oxidation

Spatial patterns in methylene blue-catalyzed oxidation of fructose at alkaline pH were found in aqueous solution and in gel systems. In a thin liquid layer (thickness >2.4 mm) a mixture of spots and stripes was formed by interaction of a nonlinear reaction and the Rayleigh or Maragoni instabilities. The pattern formation was affected by initial reactant concentrations and by the thickness of the reaction mixture layer. Long-lasting structures were formed in gel systems (polyacrylamide, agar, gelatin). These patterns also arise primarily from hydrodynamic processes.

scholarly journals The Eschenmoser coupling reaction under continuous-flow conditions

2011 ◽  
Vol 7 ◽  
pp. 1164-1172 ◽  
Author(s):  
Sukhdeep Singh ◽  
J Michael Köhler ◽  
Andreas Schober ◽  
G Alexander Groß
Keyword(s):  
Continuous Flow ◽  
Elevated Temperatures ◽  
Reaction Times ◽  
Coupling Reaction ◽  
Flow Chemistry ◽  
Flow Conditions ◽  
Reaction Conditions ◽  
Bond Forming ◽  
Carbon Carbon Bond ◽  
Reaction Proceeds

The Eschenmoser coupling is a useful carbon–carbon bond forming reaction which has been used in various different synthesis strategies. The reaction proceeds smoothly if S-alkylated ternary thioamides or thiolactames are used. In the case of S-alkylated secondary thioamides or thiolactames, the Eschenmoser coupling needs prolonged reaction times and elevated temperatures to deliver valuable yields. We have used a flow chemistry system to promote the Eschenmoser coupling under enhanced reaction conditions in order to convert the demanding precursors such as S-alkylated secondary thioamides and thiolactames in an efficient way. Under pressurized reaction conditions at about 220 °C, the desired Eschenmoser coupling products were obtained within 70 s residence time. The reaction kinetics was investigated and 15 examples of different building block combinations are given.

scholarly journals Intermolecular 3+3 Ring Expansion of Aziridines to Dehydropiperidines through the Intermediacy of Aziridinium Ylides

2019 ◽  
Author(s):  
Jennifer Schomaker ◽  
Josephine Eshon ◽  
Kate A. Nicastri ◽  
Steven C. Schmid ◽  
William T. Raskopf ◽  
...  
Keyword(s):  
Natural Product ◽  
Functional Group ◽  
Ring Expansion ◽  
Sigmatropic Rearrangement ◽  
Reactive Intermediate ◽  
Mechanistic Studies ◽  
Reaction Conditions ◽  
Complex Molecules ◽  
Form Complex ◽  
Reaction Proceeds

Bicyclic aziridines undergo formal [3+3] ring expansion reactions when exposed to rhodium-bound vinyl carbenes to form complex dehydropiperidines in a highly stereocontrolled rearrangement. Mechanistic studies and DFT computations indicate the reaction proceeds through the formation of a vinyl aziridinium ylide; this reactive intermediate undergoes a concerted, asynchronous, pseudo-[1,4]- sigmatropic rearrangement to directly furnish the heterocyclic products with net retention at the new C-C bond. In combination with an asymmetric silver-catalyzed aziridination developed in our group, this method quickly delivers enantioenriched scaffolds with up to three contiguous stereocenters. The mild reaction conditions, functional group tolerance, and high stereochemical retention of this method are especially well-suited for appending piperidine motifs to natural product and complex molecules. Ultimately, our work establishes the value of underutilized aziridinium ylides as key intermediates in strategies to convert small, strained rings to larger N-heterocycles.

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