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Study of the electrochemical behaviour of technetium on mercury in an acetic buffer medium; Etude du comportement electrochimique du technetium sur mercure en milieu acetique tamponne

Abstract

Technetium 99, produced with a high yield as fission product of {sup 235}U in nuclear reactors constitutes an important issue in the nuclear waste management. The rich and complex solution chemistry leads up to now to an insufficient knowledge of its behaviour in PUREX process and in environment. In order to understand the reduction mechanism of pertechnetate on mercury electrode, we have developed electrochemical techniques which use an additional time parameter to classical techniques used on mercury electrode. On micro-electrode, we have observed, for long time measurements (3D polarography), a split of the first polarographic wave into two waves, which characterizes the reduction of Tc(VII) in Tc(III) as well as a modification of the catalytic peak associated with technetium metal formation. moreover, differential capacitance determination of electrode/solution interface brings to the fore the existence of species (Tc(IV), T(0)) on mercury in the reduction zone corresponding to the following reductions: Tc(VII) -> T(III) and T(III) -> Tc(0). Moreover the Tc(III)/Tc(0) reduction brings the intermediary Tc(I) and Tc(II) which are present only for rates faster than the scan. Results obtained on microelectrodes have been confirmed on macro-electrode; the insoluble species Tc(IV) and Tc are formed during the reduction of Tc(VII) on metal.  More>>
Authors:
Courson, Olivier [1] 
  1. Inst. de Physique Nucleaire, Paris-11 Univ., 91 - Orsay (France)
Publication Date:
Nov 07, 1997
Product Type:
Thesis/Dissertation
Report Number:
IPNO-T-97-10
Reference Number:
SCA: 052000; PA: AIX-30:005767; EDB-99:022970; SN: 99002063925
Resource Relation:
Other Information: DN: 124 refs., 68 figs., 19 tabs.; TH: Theses (Ph.D); PBD: 7 Nov 1997
Subject:
05 NUCLEAR FUELS; ACETIC ACID; BUFFERS; ELECTROCHEMISTRY; ELECTRODES; MERCURY; PERTECHNETATES; POLAROGRAPHY; RADIOACTIVE WASTE MANAGEMENT; REDUCTION; TECHNETIUM 99
OSTI ID:
311496
Research Organizations:
Paris-11 Univ., 91 - Orsay (France)
Country of Origin:
France
Language:
French
Other Identifying Numbers:
Other: ON: DE99613706; TRN: FR9910003005767
Availability:
INIS; OSTI as DE99613706
Submitting Site:
FRN
Size:
170 p.
Announcement Date:
Mar 10, 1999

Citation Formats

Courson, Olivier. Study of the electrochemical behaviour of technetium on mercury in an acetic buffer medium; Etude du comportement electrochimique du technetium sur mercure en milieu acetique tamponne. France: N. p., 1997. Web.
Courson, Olivier. Study of the electrochemical behaviour of technetium on mercury in an acetic buffer medium; Etude du comportement electrochimique du technetium sur mercure en milieu acetique tamponne. France.
Courson, Olivier. 1997. "Study of the electrochemical behaviour of technetium on mercury in an acetic buffer medium; Etude du comportement electrochimique du technetium sur mercure en milieu acetique tamponne." France.
@misc{etde_311496,
title = {Study of the electrochemical behaviour of technetium on mercury in an acetic buffer medium; Etude du comportement electrochimique du technetium sur mercure en milieu acetique tamponne}
author = {Courson, Olivier}
abstractNote = {Technetium 99, produced with a high yield as fission product of {sup 235}U in nuclear reactors constitutes an important issue in the nuclear waste management. The rich and complex solution chemistry leads up to now to an insufficient knowledge of its behaviour in PUREX process and in environment. In order to understand the reduction mechanism of pertechnetate on mercury electrode, we have developed electrochemical techniques which use an additional time parameter to classical techniques used on mercury electrode. On micro-electrode, we have observed, for long time measurements (3D polarography), a split of the first polarographic wave into two waves, which characterizes the reduction of Tc(VII) in Tc(III) as well as a modification of the catalytic peak associated with technetium metal formation. moreover, differential capacitance determination of electrode/solution interface brings to the fore the existence of species (Tc(IV), T(0)) on mercury in the reduction zone corresponding to the following reductions: Tc(VII) -> T(III) and T(III) -> Tc(0). Moreover the Tc(III)/Tc(0) reduction brings the intermediary Tc(I) and Tc(II) which are present only for rates faster than the scan. Results obtained on microelectrodes have been confirmed on macro-electrode; the insoluble species Tc(IV) and Tc are formed during the reduction of Tc(VII) on metal. Thus, in acetate buffer media (pH=4.6), the pertechnetate reduction is characterized by the presence of absorbable species (Tc O{sub 2} hydrated,Tc). Moreover, the different electrochemical responses obtained with our techniques like 3D-polarography (waves and catalytic peaks) can be attributed to the following steps: Tc(VII)->Tc(V), Tc(IV) -> Tc(III), Tc(III) -> Tc(I) and Tc(I) -> Tc(0). The Tc(V) formation is followed by the rapid disproportionation of Tc(V) and Tc(VI) and Tc(I) reduction is associated with the proton reduction. (author) 124 refs., 68 figs., 19 tabs.}
place = {France}
year = {1997}
month = {Nov}
}