Behavior of heptavalent technetium in sulfuric acid under α-irradiation: Structural determination of technetium sulfate complexes by X-ray absorption spectroscopy and first principles calculations

I. Denden; F. Poineau; M. L. Schlegel; J. Roques; P. Lorenzo Solari; G. Blain; K. R. Czerwinski; R. Essehli; J. Barbet; M. Fattahi

doi:10.1021/jp404967f

Behavior of heptavalent technetium in sulfuric acid under α-irradiation: Structural determination of technetium sulfate complexes by X-ray absorption spectroscopy and first principles calculations

I. Denden, F. Poineau, M. L. Schlegel, J. Roques, P. Lorenzo Solari, G. Blain, K. R. Czerwinski, R. Essehli, J. Barbet, M. Fattahi

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

The effect of α-radiolysis on the behavior of heptavalent technetium has been investigated in 13 and 18 M H₂SO₄. Irradiation experiments were performed using α-particles (⁴He²⁺, E = 68 MeV) generated by the ARRONAX cyclotron. UV-visible and X-ray absorption fine structure spectroscopic studies indicate that Tc(VII) is reduced to Tc(V) under α-irradiation. Extended X-ray absorption fine structure (EXAFS) spectroscopy measurements are consistent with the presence of mononuclear technetium sulfate complexes. Experimental results and density functional calculations show the formation of [TcO(HSO₄)₃(H ₂O)(OH)]^- and/or [TcO(HSO₄)₃(H ₂O)₂] and [Tc(HSO₄)₃(SO ₄)(H₂O)] and/or [Tc(HSO₄)₃(SO ₄)(OH)]^- for 13 and 18 M H₂SO₄, respectively.

Original language	English
Pages (from-to)	1568-1575
Number of pages	8
Journal	Journal of Physical Chemistry A
Volume	118
Issue number	9
DOIs	https://doi.org/10.1021/jp404967f
State	Published - Mar 6 2014
Externally published	Yes

Funding

Funders	Funder number
U.S. Department of Energy

Access to Document

10.1021/jp404967f

Cite this

Denden, I., Poineau, F., Schlegel, M. L., Roques, J., Solari, P. L., Blain, G., Czerwinski, K. R., Essehli, R., Barbet, J., & Fattahi, M. (2014). Behavior of heptavalent technetium in sulfuric acid under α-irradiation: Structural determination of technetium sulfate complexes by X-ray absorption spectroscopy and first principles calculations. Journal of Physical Chemistry A, 118(9), 1568-1575. https://doi.org/10.1021/jp404967f

@article{b06f7e74eeb040d7b7f6cccd9d9f810a,

title = "Behavior of heptavalent technetium in sulfuric acid under α-irradiation: Structural determination of technetium sulfate complexes by X-ray absorption spectroscopy and first principles calculations",

abstract = "The effect of α-radiolysis on the behavior of heptavalent technetium has been investigated in 13 and 18 M H2SO4. Irradiation experiments were performed using α-particles (4He2+, E = 68 MeV) generated by the ARRONAX cyclotron. UV-visible and X-ray absorption fine structure spectroscopic studies indicate that Tc(VII) is reduced to Tc(V) under α-irradiation. Extended X-ray absorption fine structure (EXAFS) spectroscopy measurements are consistent with the presence of mononuclear technetium sulfate complexes. Experimental results and density functional calculations show the formation of [TcO(HSO4)3(H 2O)(OH)]- and/or [TcO(HSO4)3(H 2O)2] and [Tc(HSO4)3(SO 4)(H2O)] and/or [Tc(HSO4)3(SO 4)(OH)]- for 13 and 18 M H2SO4, respectively.",

author = "I. Denden and F. Poineau and Schlegel, {M. L.} and J. Roques and Solari, {P. Lorenzo} and G. Blain and Czerwinski, {K. R.} and R. Essehli and J. Barbet and M. Fattahi",

year = "2014",

month = mar,

day = "6",

doi = "10.1021/jp404967f",

language = "English",

volume = "118",

pages = "1568--1575",

journal = "Journal of Physical Chemistry A",

issn = "1089-5639",

publisher = "American Chemical Society",

number = "9",

}

Denden, I, Poineau, F, Schlegel, ML, Roques, J, Solari, PL, Blain, G, Czerwinski, KR, Essehli, R, Barbet, J & Fattahi, M 2014, 'Behavior of heptavalent technetium in sulfuric acid under α-irradiation: Structural determination of technetium sulfate complexes by X-ray absorption spectroscopy and first principles calculations', Journal of Physical Chemistry A, vol. 118, no. 9, pp. 1568-1575. https://doi.org/10.1021/jp404967f

Behavior of heptavalent technetium in sulfuric acid under α-irradiation: Structural determination of technetium sulfate complexes by X-ray absorption spectroscopy and first principles calculations. / Denden, I.; Poineau, F.; Schlegel, M. L. et al.
In: Journal of Physical Chemistry A, Vol. 118, No. 9, 06.03.2014, p. 1568-1575.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Behavior of heptavalent technetium in sulfuric acid under α-irradiation

T2 - Structural determination of technetium sulfate complexes by X-ray absorption spectroscopy and first principles calculations

AU - Denden, I.

AU - Poineau, F.

AU - Schlegel, M. L.

AU - Roques, J.

AU - Solari, P. Lorenzo

AU - Blain, G.

AU - Czerwinski, K. R.

AU - Essehli, R.

AU - Barbet, J.

AU - Fattahi, M.

PY - 2014/3/6

Y1 - 2014/3/6

N2 - The effect of α-radiolysis on the behavior of heptavalent technetium has been investigated in 13 and 18 M H2SO4. Irradiation experiments were performed using α-particles (4He2+, E = 68 MeV) generated by the ARRONAX cyclotron. UV-visible and X-ray absorption fine structure spectroscopic studies indicate that Tc(VII) is reduced to Tc(V) under α-irradiation. Extended X-ray absorption fine structure (EXAFS) spectroscopy measurements are consistent with the presence of mononuclear technetium sulfate complexes. Experimental results and density functional calculations show the formation of [TcO(HSO4)3(H 2O)(OH)]- and/or [TcO(HSO4)3(H 2O)2] and [Tc(HSO4)3(SO 4)(H2O)] and/or [Tc(HSO4)3(SO 4)(OH)]- for 13 and 18 M H2SO4, respectively.

AB - The effect of α-radiolysis on the behavior of heptavalent technetium has been investigated in 13 and 18 M H2SO4. Irradiation experiments were performed using α-particles (4He2+, E = 68 MeV) generated by the ARRONAX cyclotron. UV-visible and X-ray absorption fine structure spectroscopic studies indicate that Tc(VII) is reduced to Tc(V) under α-irradiation. Extended X-ray absorption fine structure (EXAFS) spectroscopy measurements are consistent with the presence of mononuclear technetium sulfate complexes. Experimental results and density functional calculations show the formation of [TcO(HSO4)3(H 2O)(OH)]- and/or [TcO(HSO4)3(H 2O)2] and [Tc(HSO4)3(SO 4)(H2O)] and/or [Tc(HSO4)3(SO 4)(OH)]- for 13 and 18 M H2SO4, respectively.

UR - http://www.scopus.com/inward/record.url?scp=84897674843&partnerID=8YFLogxK

U2 - 10.1021/jp404967f

DO - 10.1021/jp404967f

M3 - Article

C2 - 24422714

AN - SCOPUS:84897674843

SN - 1089-5639

VL - 118

SP - 1568

EP - 1575

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 9

ER -

Behavior of heptavalent technetium in sulfuric acid under α-irradiation: Structural determination of technetium sulfate complexes by X-ray absorption spectroscopy and first principles calculations

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this