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Title: Complexation of Plutonium(IV) with trans-1,2-Diaminocyclohexane-N,N,N',N'-tetraacetic Acid (CDTA) in Acidic Solution

Abstract

Understanding the interaction of Pu(IV) with complexing agents present in the nuclear fuel cycle is important for predicting the performance of used nuclear fuel separations. The complexation of Pu(IV) with trans-1,2-diaminocyclohexane-N,N,N’,N’-tetraacetic acid (CDTA) was studied in acidic solutions of 0.10 0.50 mol∙L-1 HClO4 with 1.00 mol∙L-1 (Na,H)ClO4 total ionic strength by a liquid–liquid extraction method using tracer quantities of 238Pu. The acid dissociation constants of CDTA and the autoprotolysis constant of water were determined via potentiometric titrations in 0.10–2.00 mol∙L-1 NaClO4 and 25.0 ± 0.1 °C. The variation of the dissociation constants with ionic strength was modeled with the Specific ion Interaction Theory (SIT) and the associated SIT parameters were obtained. The thermodynamic dissociation 23 constants at zero ionic strength for water and CDTA were determined from this analysis as PK$$^o_w$$ = 14.00 ± 0.03, PK$$^o_{a2}$$ = 1.52 ± 0.04, PK$$^o_{a3}$$ = 2.78 ± 0.05, PK$$^o_{a4}$$ = 4.17 ± 0.04, PK$$^o_{a5}$$ = 6.75 ± 0.02, and PK$$^o_{a6}$$ = 10.64 ± 0.04 at 25.0 ± 0.1 °C. The results of the liquid–liquid extraction experiments indicated the formation of a 1:0:1 complex, PuCDTAo, and the presence of additional protonated species, Pu(HCDTA)+ and Pu(H2CDTA)2+, at these acidities. The corresponding stability constants in 1.00 mol·L-1 (Na,H)ClO4 and 23 ± 1 °C were determined to be log10 β101=24.2 ± 0.3, log10 β111 =25.4 ± 0.2, and log10 β121 = 25.8 ± 0.1.

Authors:
 [1];  [2];  [2]; ORCiD logo [1]
  1. Washington State Univ., Pullman, WA (United States). Dept. of Chemistry
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Glenn T. Seaborg Inst., Physical and Life Sciences
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Washington State Univ., Pullman, WA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Nuclear Energy (NE)
OSTI Identifier:
1548379
Alternate Identifier(s):
OSTI ID: 1529249
Report Number(s):
LLNL-JRNL-776832
Journal ID: ISSN 0095-9782; 969848
Grant/Contract Number:  
AC52-07NA27344; NA0002916
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Solution Chemistry
Additional Journal Information:
Journal Volume: 48; Journal Issue: 2; Journal ID: ISSN 0095-9782
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS; Plutonium(IV); CDTA; Complexation; Stability Constant; Liquid Liquid Extraction; Specific ion Interaction Theory

Citation Formats

Friend, Mitchell T., Zhao, Pihong, Zavarin, Mavrik, and Wall, Nathalie A. Complexation of Plutonium(IV) with trans-1,2-Diaminocyclohexane-N,N,N',N'-tetraacetic Acid (CDTA) in Acidic Solution. United States: N. p., 2019. Web. doi:10.1007/s10953-019-00859-1.
Friend, Mitchell T., Zhao, Pihong, Zavarin, Mavrik, & Wall, Nathalie A. Complexation of Plutonium(IV) with trans-1,2-Diaminocyclohexane-N,N,N',N'-tetraacetic Acid (CDTA) in Acidic Solution. United States. doi:10.1007/s10953-019-00859-1.
Friend, Mitchell T., Zhao, Pihong, Zavarin, Mavrik, and Wall, Nathalie A. Mon . "Complexation of Plutonium(IV) with trans-1,2-Diaminocyclohexane-N,N,N',N'-tetraacetic Acid (CDTA) in Acidic Solution". United States. doi:10.1007/s10953-019-00859-1. https://www.osti.gov/servlets/purl/1548379.
@article{osti_1548379,
title = {Complexation of Plutonium(IV) with trans-1,2-Diaminocyclohexane-N,N,N',N'-tetraacetic Acid (CDTA) in Acidic Solution},
author = {Friend, Mitchell T. and Zhao, Pihong and Zavarin, Mavrik and Wall, Nathalie A.},
abstractNote = {Understanding the interaction of Pu(IV) with complexing agents present in the nuclear fuel cycle is important for predicting the performance of used nuclear fuel separations. The complexation of Pu(IV) with trans-1,2-diaminocyclohexane-N,N,N’,N’-tetraacetic acid (CDTA) was studied in acidic solutions of 0.10 0.50 mol∙L-1 HClO4 with 1.00 mol∙L-1 (Na,H)ClO4 total ionic strength by a liquid–liquid extraction method using tracer quantities of 238Pu. The acid dissociation constants of CDTA and the autoprotolysis constant of water were determined via potentiometric titrations in 0.10–2.00 mol∙L-1 NaClO4 and 25.0 ± 0.1 °C. The variation of the dissociation constants with ionic strength was modeled with the Specific ion Interaction Theory (SIT) and the associated SIT parameters were obtained. The thermodynamic dissociation 23 constants at zero ionic strength for water and CDTA were determined from this analysis as PK$^o_w$ = 14.00 ± 0.03, PK$^o_{a2}$ = 1.52 ± 0.04, PK$^o_{a3}$ = 2.78 ± 0.05, PK$^o_{a4}$ = 4.17 ± 0.04, PK$^o_{a5}$ = 6.75 ± 0.02, and PK$^o_{a6}$ = 10.64 ± 0.04 at 25.0 ± 0.1 °C. The results of the liquid–liquid extraction experiments indicated the formation of a 1:0:1 complex, PuCDTAo, and the presence of additional protonated species, Pu(HCDTA)+ and Pu(H2CDTA)2+, at these acidities. The corresponding stability constants in 1.00 mol·L-1 (Na,H)ClO4 and 23 ± 1 °C were determined to be log10 β101=24.2 ± 0.3, log10 β111 =25.4 ± 0.2, and log10 β121 = 25.8 ± 0.1.},
doi = {10.1007/s10953-019-00859-1},
journal = {Journal of Solution Chemistry},
number = 2,
volume = 48,
place = {United States},
year = {2019},
month = {2}
}

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