Gamma-radiolysis of ferric ethylene diamine tetra-acetate in neutral aqueous solution

Kundu, K.P.; Matsuura, Niro

doi:10.1016/0020-7055(75)90021-2

Cited by 20 publications

(8 citation statements)

References 8 publications

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“…HO • initially oxidizes ligand by H-abstraction, followed by either further oxidation by intra-molecular electron transfer (to yield Fe(II)L Ox ) or intermolecular electron transfer from Fe(III)L to yield Fe(II)L + Fe(III)L Ox (Kundu and Matsuura, 1975;Rahhal and Richter, 1989). Alternatively O 2 may oxidize this radical in a similar fashion to uncomplexed EDTA (Höbel and von Sonntag, 1998) Zepp et al (1992) with the assumption that the initial organic radical formed is rapidly oxidized by O 2 to yield O…”

Section: Kinetics Of Fe(ii) Oxidation and Ho • Production By Fe(ii)edmentioning

confidence: 99%

Importance of Iron Complexation for Fenton-Mediated Hydroxyl Radical Production at Circumneutral pH

2016

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The reaction between Fe(II) and H 2 O 2 to yield hydroxyl radicals (HO • ), the Fenton reaction, is of interest due to its role in trace metal and natural organic matter biogeochemistry, its utility in water treatment and its role in oxidative cell degradation and associated human disease. There is significant dispute over whether HO • , the most reactive of the so-called reactive oxygen species (ROS), is formed in this reaction, particularly under circumneutral conditions relevant to natural systems. In this work we have studied the oxidation kinetics of Fe(II) complexed by L = citrate, ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) and also measured HO • production using phthalhydrazide as a probe compound at pH 8.2. A kinetic model has been developed and utilized to confirm that HO • is the sole product of the Fe(II)L-H 2 O 2 reaction for L = EDTA and DTPA. Quantitative HO • production also appears likely for L = citrate, although uncertainties with the speciation of Fe(II)-citrate complexes as well as difficulties in modeling the oxidation kinetics of these complexes has prevented a definitive conclusion. In the absence of ligands at circumneutral pH, inorganic Fe(II) reacts with H 2 O 2 to yield a species other than HO • , contrary to the well-established production of HO • from inorganic Fe(II) at low pH. Our results suggest that at high pH Fe(II) must be complexed for HO • production to occur.

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Section: Kinetics Of Fe(ii) Oxidation and Ho • Production By Fe(ii)edmentioning

confidence: 99%

Importance of Iron Complexation for Fenton-Mediated Hydroxyl Radical Production at Circumneutral pH

2016

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“…Some studies investigated the effect of the ligand complexation in aqueous solution. [61][62][63][64][65][66][67][68][69][70] For example, for DTPA (Diethylene Triamine Penta-acetic Acid) in aqueous solution, it has been observed that the degradation radiolytic yield for uncomplexed DTPA is higher than that for the Sm-DTPA complex. The authors suggest that the coordination of the carboxyl group to the metal would increase the rigidity of the ligand which prevents the formation of the intermediate or would hinder the decarboxylation of the radical-complex.…”

Section: Introductionmentioning

confidence: 99%

Effect of metal complexation on diglycolamide radiolysis: a comparison between ex situ gamma and in situ alpha irradiation

Kimberlin

Saint-Louis

Guillaumont

et al. 2022

Phys. Chem. Chem. Phys.

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“…The majority of actinide radiation chemistry knowledge is concentrated toward the beginning of the series, − for which radiation-induced reactions have been demonstrated to significantly impact the accessibility and lifetime of actinide oxidation states at both ultrafast (pico- to microseconds) − and steady-state timescales. − Furthermore, there is precedence for these radiation-induced actinide redox reactions altering the radiolytic integrity of their corresponding complexes, relative to the free ligand, through facilitation of inner- versus outer-sphere reaction pathways. − Concerning the late actinidesamericium (Am) onwardminimal information is available, and yet it remains an area of significant fundamental interest owing to paradigm shifts in the oxidation state metastability from trivalency to divalency in californium (Cf), − and an accessible tetravalent state for berkelium (Bk) . Both of these redox states are at odds to their predominantly trivalent neighbors, Am and curium (Cm) .…”

Section: Introductionmentioning

confidence: 99%

Transient Radiation-Induced Berkelium(III) and Californium(III) Redox Chemistry in Aqueous Solution

et al. 2022

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Despite the significant impact of radiation-induced redox reactions on the accessibility and lifetimes of actinide oxidation states, fundamental knowledge of aqueous actinide metal ion radiation chemistry is limited, especially for the late actinides. A quantitative understanding of these intrinsic radiation-induced processes is essential for investigating the fundamental properties of these actinides. We present here a picosecond electron pulse reaction kinetics study into the radiation-induced redox chemistry of trivalent berkelium (Bk(III)) and californium (Cf(III)) ions in acidic aqueous solutions at ambient temperature. New and first-of-a-kind, second-order rate coefficients are reported for the transient radical-induced reduction of Bk(III) and Cf(III) by the hydrated electron (eaq –) and hydrogen atom (H•), demonstrating a significant reactivity (up to 1011 M–1 s–1) indicative of a preference of these metals to adopt divalent states. Additionally, we report the first-ever second-order rate coefficients for the transient radical-induced oxidation of these elements by a reaction with hydroxyl (•OH) and nitrate (NO3 •) radicals, which also exhibited fast reactivity (ca. 108 M–1 s–1). Transient Cf(II), Cf(IV), and Bk(IV) absorption spectra are also reported. Overall, the presented data highlight the existence of rich, complex, intrinsic late actinide radiation-induced redox chemistry that has the potential to influence the findings of other areas of actinide science.

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Gamma-radiolysis of ferric ethylene diamine tetra-acetate in neutral aqueous solution

Cited by 20 publications

References 8 publications

Importance of Iron Complexation for Fenton-Mediated Hydroxyl Radical Production at Circumneutral pH

Importance of Iron Complexation for Fenton-Mediated Hydroxyl Radical Production at Circumneutral pH

Effect of metal complexation on diglycolamide radiolysis: a comparison between ex situ gamma and in situ alpha irradiation

Transient Radiation-Induced Berkelium(III) and Californium(III) Redox Chemistry in Aqueous Solution

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