Kinetic and Thermodynamic Aspects of Tracer-Scale and Single Atom Chemistry

Guillaumont, R.; Adloff, J.P.; Peneloux, André

doi:10.1524/ract.1989.46.4.169

Cited by 64 publications

(28 citation statements)

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“…Does it make sense, then, to study chemical equilibria with a single atom? Guillaumont et al [45,46], in view of this dilemma, have pointed out that chemical speciation of nuclides at the tracer scale is usually feasible with partition methods in which the species to be characterized is distributed between two phases. This can be an aqueous and an organic phase or a solid and a gas phase.…”

Section: Single-atom Chemistrymentioning

confidence: 99%

“…This can be an aqueous and an organic phase or a solid and a gas phase. According to [45], single-atom chemistry requires the introduction of a specific thermodynamic function, the single-particle free energy. An expression equivalent to the law of mass action is derived in [45] in which activities (concentrations or partial pressures) are replaced by the probability of finding the species in the appropriate phase.…”

Section: Single-atom Chemistrymentioning

confidence: 99%

“…According to [45], single-atom chemistry requires the introduction of a specific thermodynamic function, the single-particle free energy. An expression equivalent to the law of mass action is derived in [45] in which activities (concentrations or partial pressures) are replaced by the probability of finding the species in the appropriate phase. According to this law, an equilibrium constant (i.e., the distribution coefficient K d of M between two phases) is correctly defined in terms of the probabilities of finding M in one phase or the other.…”

Section: Single-atom Chemistrymentioning

confidence: 99%

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Critical evaluation of the chemical properties of the transactinide elements (IUPAC Technical Report)

Kratz¹

2003

Pure and Applied Chemistry

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Names of countries given after Members' names are in accordance with the IUPAC Handbook 1998Handbook -1999. Republication Abstract: In this paper, the chemical properties of the transactinide elements rutherfordium, Rf (element 104); dubnium, Db (element 105); and seaborgium, Sg (element 106) are critically reviewed. The experimental methods for performing rapid chemical separations on a time scale of seconds are reviewed, and comments are given on the special situation with the transactinides for which the chemistry has to be studied with single atoms. There follows a systematic description of theoretical predictions and experimental results on the chemistry of Rf, Db, and Sg-their mutual comparison and evaluation. The literature cited has the cutoff date of March 1999. The more recent chemical identification of bohrium, Bh (element 107), and of hassium, Hs (element 108), should be evaluated in a future Part II of this report.

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Section: Single-atom Chemistrymentioning

confidence: 99%

Section: Single-atom Chemistrymentioning

confidence: 99%

Section: Single-atom Chemistrymentioning

confidence: 99%

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Critical evaluation of the chemical properties of the transactinide elements (IUPAC Technical Report)

Kratz¹

2003

Pure and Applied Chemistry

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“…The atom studied cannot interact with other atoms of the same element but instead it only interacts with its surroundings, because no macroscopic amounts of the element are present. To obtain reliable results, it is necessary to select a chemical system in which one atom undergoes the same kind of interaction many times [1]. Liquid-liquid extraction is a good example of such a system, and this technique has been extensively used for the study of the lighter transactinide elements [2].…”

Section: Introductionmentioning

confidence: 99%

Extraction of short-lived zirconium and hafnium isotopes using crown ethers: A model system for the study of rutherfordium

Sudowe¹,

Calvert²,

Düllmann³

et al. 2006

Radiochimica Acta

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Zirconium / Hafnium / Crown ether / Liquid-liquid extraction / Distribution ratio / Separation factor SummaryThe extraction of zirconium and hafnium from hydrochloric acid media was studied using the crown ethers dibenzo-18-crown-6 (DB18C6), dicyclohexano-18-crown-6 (DC18C6) and dicyclohexano-24-crown-8 (DC24C8) as extractants. The goal was to find an extraction system that exhibits a high selectivity between the members of group 4 of the periodic table and is suitable for the study of rutherfordium. It was found Rf.

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“…Adloff and Guillaumont (31) have thoroughly discussed the validity of conclusions about chemical behavior obtained from very small numbers of atoms. They defined an equilibrium constant for such reactions in terms of the probabilities of finding the species in one phase or the other and concluded that it is valid to combine the results of many separate oneatom-at-a-time experiments in order to get statistically significant results (32,33).…”

Section: Chemical Separation Methodsmentioning

confidence: 99%

Chemistry of the Heaviest Elements- One Atom at a Time

Hoffman

Lee

1999

J. Chem. Educ.

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FutureMore "In-Depth" Chemical Studies Chemistry beyond Seaborgium? 93 NpIn keeping with the goal of the Viewpoints series of the Journal of Chemical Education, this article gives a 75-year perspective of the chemistry of the heaviest elements, including a 50-year retrospective view of past developments, a summary of current research achievements and applications, and some predictions about exciting, new developments that might be envisioned within the next 25 years. A historical perspective of the importance of chemical separations in the discoveries of the transuranium elements from neptunium (Z = 93) through mendelevium (Z = 101) is given. The development of techniques for studying the chemical properties of mendelevium and still heavier elements on the basis of measuring the radioactive decay of a single atom ("atom-at-a-time" chemistry) and combining the results of many separate experiments is reviewed. The influence of relativistic effects (expected to increase as Z 2 ) on chemical properties is discussed. The results from recent atom-at-a-time studies of the chemistry of the heaviest elements through seaborgium (Z = 106) are summarized and show that their properties cannot be readily predicted based on simple extrapolation from the properties of their lighter homologues in the periodic table. The prospects for extending chemical studies to still heavier elements than seaborgium are considered and appear promising.

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Kinetic and Thermodynamic Aspects of Tracer-Scale and Single Atom Chemistry

Cited by 64 publications

References 1 publication

Critical evaluation of the chemical properties of the transactinide elements (IUPAC Technical Report)

Critical evaluation of the chemical properties of the transactinide elements (IUPAC Technical Report)

Extraction of short-lived zirconium and hafnium isotopes using crown ethers: A model system for the study of rutherfordium

Chemistry of the Heaviest Elements- One Atom at a Time

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