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Abstract  

Extraction of microamounts of calcium and strontium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H+B) in the presence of diphenyl-N,N-dibutylcarbamoylmethyl phosphine oxide (DPDBCMPO, L) has been investigated. The equilibrium data have been explained assuming that the species HL+,
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $${\text{HL}}_{2}^{ + }$$ \end{document}
, CaL2+,
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $${\text{CaL}}_{ 2}^{{ 2 { + }}}$$ \end{document}
,
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $${\text{CaL}}_{ 3}^{{ 2 { + }}}$$ \end{document}
, SrL2+,
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $${\text{SrL}}_{ 2}^{{ 2 { + }}}$$ \end{document}
,
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $${\text{SrL}}_{ 3}^{{ 2 { + }}}$$ \end{document}
and
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $${\text{SrL}}_{ 4}^{{ 2 { + }}}$$ \end{document}
are extracted into the organic phase. The values of extraction and stability constants of the cationic complexes in nitrobenzene saturated with water have been determined. In the considered nitrobenzene medium, it was found that the stability constants of the complexes CaL2+,
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $${\text{CaL}}_{ 2}^{{ 2 { + }}}$$ \end{document}
and
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $${\text{CaL}}_{ 3}^{{ 2 { + }}}$$ \end{document}
, where L is DPDBCMPO, are somewhat higher than those of the corresponding complex species SrL2+,
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $${\text{SrL}}_{ 2}^{{ 2 { + }}}$$ \end{document}
and
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $${\text{SrL}}_{ 3}^{{ 2 { + }}}$$ \end{document}
.
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Abstract  

Extraction of microamounts of europium and americium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H+B) in the presence of N,N,N′,N′-tetraethyl-2,6-dipicolinamide (TEtDPA, L) has been investigated. The equilibrium data have been explained assuming that the cations HL+, HL2 3+, ML2 3+ and ML3 3+ (M3+ = Eu3+, Am3+) are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated with water have been determined. It has been found that the stability constants of the corresponding complexes EuLn,org 3+ and AmLn,org 3+, where n = 2, 3 and L is TEtDPA, in the mentioned medium are comparable.

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Abstract  

The oxidation of aliphatic thiols by air oxygen under mild conditions catalyzed by copper(II) complexes with amines (e.g. benzylamine) has been investigated. It was found that the reaction proceeds as a conjugated oxidation of both amines and thiols. The products of transformation of benzylamine have been identified. Copper(I) dodecanethiolate was synthesized for the first time, and its composition was determined. The thiolate is shown to be an intermediate of the process in the systems which demonstrate low activity. The intermediate in the most active systems is a mixed-ligand copper(II) complex containing both molecules of amine and thiolate anions in the coordination sphere.

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Abstract  

Extraction of microamounts of europium and americium by a phenyltrifluoromethyl sulfone (FS 13) solution of hydrogen dicarbollylcobaltate (H+B) in the presence of N,N′-diethyl-N,N′-diphenyl-2,6-dipicolinamide (EtPhDPA, L) has been investigated. The equilibrium data have been explained assuming that the species HL+, HL2 +, ML2 3+, ML3 3+ and ML4 3+ (M3+ = Eu3+, Am3+) are extracted into the organic phase. The values of extraction and stability constants of the cationic complexes in FS 13 saturated with water have been determined. It was found that the stability constants of the corresponding complexes EuLn 3+ and AmLn 3+, where n = 2, 3, 4 and L is EtPhDPA, in water-saturated FS 13 are comparable.

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Abstract  

Extraction of microamounts of europium and americium by a phenyltrifluoromethyl sulfone (FS 13) solution of hydrogen dicarbollylcobaltate (H+B) in the presence of N,N,N′,N′-tetraethyl-2,6-dipicolinamide (TEtDPA, L) has been investigated. The equilibrium data have been explained assuming that the species HL+,
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $${\text{HL}}_{ 2}^{ + } ,$$ \end{document}
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $${\text{ML}_{2}^{3 +}}$$ \end{document}
and
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $${\text{ML}_{ 3}^{ 3+}}$$ \end{document}
(M3+ = Eu3+, Am3+) are extracted into the organic phase. The values of extraction and stability constants of the cationic complex species in FS 13 saturated with water have been determined. It was found that the stability constants of the corresponding complexes
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $${\text{EuL}}_{n}^{ 3+ }$$ \end{document}
and
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $${\text{AmL}}_{n}^{ 3+ }$$ \end{document}
, where n = 2, 3 and L is TEtDPA, in the mentioned FS 13 medium are comparable.
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Abstract  

Extraction of microamounts of calcium and strontium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H+B) in the presence of N,N,N′,N′-tetraisobutyl-2,6-dipicolinamide [T(iBu)DPA, L] has been investigated. The equilibrium data have been explained assuming that the species HL+, HL2 +, CaL2 2+, SrL2 2+ and SrL3 2+ are extracted into the organic phase. The values of extraction and stability constants of the cationic complexes in nitrobenzene saturated with water have been determined.

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Journal of Radioanalytical and Nuclear Chemistry
Authors: G. F. Egorov, G. P. Tkhorgnitsky, V. N. Romanovskiy, V. A. Babain, I. V. Smirnov, J. D. Law, R. S. Herbst, and T. A. Todd

Summary  

The radiation stability of UNEX stripping solutions containing water, methylamine carbonate, nitrilotriacetic acid, and metal salts was experimentally studied. The decomposition of the methylamine carbonate and nitrilotriacetic acid under gamma irradiation (dose: 0.29 kGy) is lower than 0.5 molecules per 100 eV or about 7.2E-04% and 0.047%, respectively. The decomposition products do not adversely affect the UNEX process up to a 3 MGy absorbed dose. The stripping solutions can be regenerated and reused.

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Summary  

Scientists at the Idaho National Laboratory (INL) and Khlopin Radium Institute (KRI) collaboratively developed and validated the concept of a Universal Extraction (UNEX) process for simultaneously removing the major radionuclides (Cs, Sr, actinides, and lanthanides) from acidic radioactive waste in a single solvent extraction process. The process chemistry is unique and complicated, since the extractants, chlorinated cobalt dicarbollide (CCD), polyethylene glycol (PEG), and diphenyl-N,N-di-n-butylcarbamoylmethylphosphine oxide (Ph2CMPO), operatesynergistically to extract the major radionuclides.A combination of classical chemistry techniques, infrared (IR) spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy were utilized to identify and explain the structures formed in the organic phase with protons or metal ions. Model systems, CCD-PEG and CCD-bidentate organophosphorus compounds were studied and possible structures of complexes, existing in the organic phase, are proposed and properties of the UNEX extractant are discussed.

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