The Chemistry of Superheavy Elements

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The Chemistry of Superheavy Elements
Edited by

Gesellschaft für Schwerionenforschung mbH (GSI), Darmstadt, Germany


eBook ISBN: Print ISBN:

0-306-48415-3 1-4020-1250-0

©2004 Kluwer Academic Publishers New York, Boston, Dordrecht, London, Moscow Print ©2003 Kluwer Academic Publishers Dordrecht All rights reserved No part of this eBook may be reproduced or transmitted in any form or by any means, electronic, mechanical, recording, or otherwise, without written consent from the Publisher Created in the United States of America Visit Kluwer Online at: and Kluwer's eBookstore at:


Preface Chapter 1 Properties and Syntheses of Superheavy Elements S. Hofmann Theoretical Chemistry of the Heaviest Elements V. Pershina Fundamental Aspects of Single Atom Chemistry D. Trubert, C. Le Naour Experimental Techniques A. Türler, K.E. Gregorich Liquid-Phase Chemistry J.V. Kratz Gas-Phase Adsorption Chromatographic Determination of Thermochemical Data and Empirical Methods for their Estimation B. Eichler, R. Eichler Gas-Phase Chemistry H.W. Gäggeler, A. Türler Historical Reminiscences G. Herrmann

vii 1

Chapter 2


Chapter 3


Chapter 4


Chapter 5


Chapter 6


Chapter 7


Chapter 8


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for those chemists and physicists who are not experts in the field and for our interested fellow scientists in adjacent fields. as a self contained topic. It is written for those – students and novices -.who begin to work and those who are working in this fascinating and challenging field of the heaviest and superheavy elements. Special emphasis is laid on an extensive coverage of the original literature in the reference part of each of the eight chapters to facilitate further and deeper studies of specific aspects. Superheavy elements – chemical elements which are much heavier than those which we know of from our daily life – are a persistent dream in human minds and the kernel of science fiction literature for about a century. their advisers and for the practicing scientists in the field – chemists and physicists . for their the most complete source of reference about our today's knowledge of the chemistry of transactinides and superheavy elements. besides a number of very detailed discussions for the experts this book shall also provide interesting and easy to read material for teachers who are interested in this subject. including important related nuclear aspects. The index for each chapter should provide help to easily find a desired topic and to use this book as a convenient source to get fast access to a desired topic. However.Preface This book is the first to treat the chemistry of superheavy elements. This book describes in Chapter 1 how today this dream becomes true at a .

From this point of view there are good arguments to begin the series of superheavy elements with element 104. we know of 112 chemical elements. are connecting the region of shell-stabilized spherical nuclei around element 114 to our known world. The appealing aspect of having the superheavy elements begin at element 104 is that this is identical with the beginning of the series of transactinide elements. one century after Ernest Rutherford and Frederick Soddy postulated that in the radioactive decay one chemical element transmutes into a new one. which surfaced during the mid-50s. all the way to the beginning of the current research programs described in Chapter 1. The last chapter outlines historical developments. It also discusses experimental attempts and prospects of the search for superheavy elements in Nature. Now where are superheavy elements located on a physicist's chart of nuclides and on the Periodic Table of the Elements -. are used with an equal meaning in this book. This is 16 orders of magnitude longer than the expected nuclear lifetime of s these isotopes would survive without any extra shell stabilization. what the tools are to synthesize these elusive. others have widened this region and have included lighter elements. By now. The terms "superheavy elements" and "transactinide elements". the world of chemical elements would be terminated at the end of the actinides. from first scientifically sound ideas about the existence of superheavy elements. Taking s as a realistic limit for a minimum lifetime of a system which can be called a chemical element. It is generally agreed that the term "superheavy element" is a synonym for elements which exist solely due to their nuclear shell effects. some authors are still using the term "superheavy element" in its traditional form. . The discoveries of elements 114 and 116 are currently waiting to be confirmed and experimentalists are embarking to discover new and heavier elements. At that time this island of stability was believed to be surrounded by a "sea of instability". paved with cobblestones of shell-stabilized deformed nuclei. rutherfordium. this sea has drained off and sandbanks and rocky footpaths. and assuming the absence of any shell effects. Perfectly acceptable. as shown in Chapter 1. The current status of experimental and theoretical insights into this very unique region of nuclear stability is briefly reviewed. in short "transactinides".the most basic chart in chemistry? The term "superheavy elements" was first coined for elements on a remote "island of stability" around atomic number 114 (Chapter 8). Because of the extra stability from nuclear shell-effects the known isotopes of rutherfordium exhibit half-lives of up to one minute. Today.viii The Chemistry of Superheavy Elements few accelerator laboratories. man-made elements in heavy-ion nuclear reactions and how to detect the specific nuclear decays which terminate their existence shortly after they are created.

It is quite natural that there is a large body of information on group-4 element 104. where especially up to date molecular calculations dramatically increased our insights over the last decade. One century after the beginning of most dramatic changes in physics and chemistry. It is demonstrated in Chapter 4 how this can be achieved. A large variety of tools. The actual state of the theoretical chemistry of the heaviest elements is comprehensively covered in Chapter 2. from manual separation procedures to very sophisticated. short-lived atoms establishes one of the most extreme limits in chemistry. automated computer-controlled apparatuses have been developed and are now at hand to study the chemical properties of these short-lived elements one-atom-at-a-time in the liquid phase and in the gas phase. modern relativistic atomic and molecular calculations clearly show the very strong influence of direct and indirect relativistic effects not only on electronic configurations but also on chemical properties of the heaviest elements. The known chemical properties of superheavy elements are presented and discussed in Chapter 5 and 7 based upon experimental results obtained from the liquid phase and from the gas phase. what kinds of set-ups are presently available and what the prospects are for future developments to further expand our knowledge. dubnium. and group-5 element 105. reversible processes Chapter 3 discusses specific aspects how the behavior of single atoms mirrors properties of macro amounts. It does not only discuss most recent theoretical developments and results.Preface ix One of the most important and most fascinating questions for a chemist is the one about the position of the superheavy elements in the Periodic Table of the Elements. While large numbers of atoms and molecules are deeply inherent in the statistical approach to understanding chemical reactions as dynamic.M. recent detailed studies demonstrate that these . respectively. after the advent of quantum theory and in the year of the anniversary of Paul A. which are now under investigation for three decades. how well accommodates the Periodic Table these elements as transition metals in the seventh period. However. Do the rules of the Periodic Table still hold for the heaviest elements? What is a valid architecture of the Periodic Table at its upper end? The main body of information to answer this question from our today's knowledge of the chemistry of superheavy or transactinide elements is embraced between the two mainly "nuclear" oriented chapters at the beginning and at the end. The chemistry of superheavy elements always faces a one-atom-at-a-time situation – performing separations and characterizations of an element with single. rutherfordium. Dirac. but it also relates these results to experimental observations.

presumably due to strong influence of relativistic effects? Empirical models are frequently applied in chemistry to relate experimental observations to physicochemical or thermodynamical quantities. Even more challenging. Matthias Schädel Darmstadt and Wiesbaden December 2002 . and especially for her work on some of the graphics and for preparing the final format. The individual chapters were finished between mid of the year and November of the year 2002. These empirical procedures and correlations are outlined in Chapter 6 for a deeper understanding of one of the possible ways to interpret experimental findings from gas phase chemistry. The chemistry of element 106. hassium. at least one experiment indicated a deviation from an extrapolation in group 6. This is presented in Chapter 7 together with an attempt to get a first glimpse of the chemical property of element 112. While most of them revealed a "surprisingly normal" behavior.gsi. Last. This has extensively been used over several decades for the interpretation of experimental results obtained from gas phase adsorption processes and is still used to interpret the gas chromatographic results discussed in Chapter 7. seaborgium. Pictures of the people involved in many of the described experiments.x The Chemistry of Superheavy Elements elements still hold many surprises. All the authors of the individual chapters are describing the up-to-date ongoing research in their field where they are leading experts and give a thorough and comprehensive review of our today's Only thanks to them was it possible to provide such a far-reaching coverage of the chemistry of superheavy elements. performed in one gas phase experiment each. Many thanks go to the authors of the individual chapters who enthusiastically agreed to contribute to this book and who spent so much time and effort to collect. judge and write up exten­ sive amounts of material. was first tackled in 1995 followed by a series of experiments in the aqueous and the gas phase. Will it chemically react like mercury or will it be much more inert. They sometimes exhibit rather unexpected properties. were recent investigations on elements 107. photos of the instruments and more details on experiments and results can be found on the web-page http://www. I wish to acknowledge the contributions of Jan Willem Wijnen and Emma Roberts from the Kluwer Academic Publishers who started (JWW) and finalized (ER) this project with me. its a great pleasure to thank Brigitta Schausten very much for helping me and the authors with hundreds of smaller or larger details which came up during the preparation of this book. and 108. but definitely not least. because of the only very few numbers of atoms produced per day. bohrium.

Chapter 1 Properties and Syntheses of Superheavy Elements S. the strength of the attractive nuclear force which binds neutrons and protons together and creates a surface tension and the repulsive electric force. Introduction Searching for new chemical elements is an attempt to answer questions of partly fundamental character: How many elements may exist? How long is their lifetime? Which properties determine their stability? How can they be synthesized? What are their chemical properties? How are the electrons arranged in the strong electric field of the nucleus? Searching for new elements beyond uranium by the process of neutron decay. and it was shown that fission will most likely limit the number of chemical elements. Frisch [2]. Meitner and O. Hofmann Gesellschaft für Schwerionenforschung mbH.R. the maximum number of elements was expected to be about 100." This was the correct interpretation given by L. 1-29. Germany 1. By applying the existing charged liquid-drop model of the nucleus [3. At that time. nuclear fission was explained quite naturally. D-64221 Darmstadt. The Chemistry of Superheavy Elements. 1 M. Hahn and F. .).4]. © 2003 Kluwer Academic Publishers. This number results from the balance of two fundamental nuclear parameters. Printed in the Netherlands. and the term "fission" was coined for this process. Planckstasse 1. Schädel (ed. Straßmann [1] discovered capture and succeeding the possibility that a heavy nucleus might "divide itself into two nuclei. O.

Amongst other special properties. and the identification of the nuclei by generic ties to known daughter decays after implantation into position-sensitive detectors [13-15]. . However. SHEs.) Experiments are presented. was less problematic than the calculation of the stability of those doubly closed shell nuclei against fission. and attempts have been made to discover naturally occurring SHEs. As a consequence. 28. the doubly magic nuclei are spherical and resist deformation. The magic numbers were successfully explained by the nuclear shell model [5. N = 126 is also identified as a magic number. see also Chapter 8. was critically debated. but show non-uniformities as evidenced by variations in the measured atomic masses. At the magic proton or neutron numbers 2. was coined for these elements. However. Instead of 126 for the protons also 114 or 120 were calculated as closed shells.6].2 The Chemistry of Superheavy Elements The properties of nuclei are not smooth uniform functions of the proton and neutron numbers. 20. as soon as experiments could be performed without technical limitations. although not unambiguous. The numbers 126 for the protons and 184 for the neutrons were predicted to be the next shell closures. In the following sections a detailed description is given of the set-ups of the physical experiments used for the investigation of SHEs. 8. in which cold and hot fusion reactions were used for the synthesis of SHEs.form closed shells called “magic” numbers. Some of the half-lives approached the age of the universe. and an extrapolation into unknown regions was reasonable. predicted half-lives based on various calculations differed by many orders of magnitude [7-12]. The term superheavy elements. none could be substantiated after more detailed inspection. For neutrons. fusion or transfer of nucleons. the highest stability is observed in the case of the "doubly magic" nuclei with a closed shell for both protons and neutrons. also the nucleons in a nucleus . it turned out that the most successful methods for the laboratory synthesis of heavy elements are fusion-evaporation reactions using heavy-element targets. the survival of the compound nuclei formed after complete fusion was difficult to predict.described by quantum mechanical laws . Closely related to the fission probability of SHEs in the ground-state. Like the electrons in an atom. Although discoveries were announced from time to time. There was also great uncertainty of the production yields for SHEs. Even the best choice of the reaction mechanism. (The instrumentation based on chemical methods for the study of heavy elements is presented in subsequent chapters of this book. 50. recoil-separation techniques. and 82. see Chapter 8. the nuclei have an increased binding energy relative to the average trend. The prediction of magic numbers.

the yield as a function of the beam energy. which influence the yield for the synthesis of SHEs. and symmetric combinations like tin plus tin up to samarium plus samarium. some isotopes can be produced in amounts of kilograms or at least grams. in Darmstadt. neutron decay made it possible to capture in high-flux reactors and successive climb up the Periodic Table element by element. Properties and Syntheses of Superheavy Elements 3 These experiments resulted in the identification of elements 107 to 112 at the Gesellschaft für Schwerionenforschung. The data are obtained by measuring excitation functions. Finally. targets of lead and bismuth irradiated by projectiles from calcium to krypton. Experimental Techniques 2. Moreover. In subsequent sections a theoretical description follows discussing properties of nuclei in the region of SHEs and phenomena. Also inverse . which results (using thicker targets) in an energy distribution that is too wide for both the production of fusion products and their in-flight separation. the bombardment of heavy-element targets with heavy ions from an accelerator. While from neptunium to californium. the use of thin targets in combination with well defined beam energies from accelerators results in unique information about the reaction mechanism. LBNL. Sufficiently thick enough targets cannot be manufactured from these elements. which started in 1999 at Lawrence Berkeley National Laboratory. GSI. however. in Dubna.1 TARGETS AND ACCELERATORS Transuranium elements are always man-made. JINR. only thin targets of the order of 1 can be used. respectively. Various combinations of projectiles and targets are in principle possible for the synthesis of heavy elements: actinide targets irradiated by light projectiles of elements in the range from neon to calcium.1. Empirical descriptions of hot and cold fusion nuclear reaction systematic are outlined. On the other hand. and are available only in quantities of micrograms and picograms. Up to fermium. The cross section is less than in the case of neutron capture and values are considerably below the geometrical size of the nuclei. a summary and outlook is given. and in the recent synthesis of elements 114 and 116 at the Joint Institute for Nuclear Research. the two heaviest species. the method ends due to the lack of decay and too short and fission halflives of the heavier elements. At fermium. This limitation arises from the energy loss of the ion beam in the target. We also report on a search for element 118. The region beyond fermium is best accessible using heavy-ion fusion reactions. 2. in Berkeley.

France. In the early 1960s physical techniques were developed which allowed for detection of nuclei with lifetimes of less than one second at high sensitivity. Beam currents of several particle particles/s) are presently reached. Italy and Japan are similar and are usually made in close collaboration and exchange of know-how. the UNILAC (UNIversal Linear Accelerator) was constructed in Darmstadt. In order to compensate for the decreasing cross sections of the synthesis of heavy elements. later upgraded to the SuperHILAC. Germany. Such microamperes high currents. Aiming at the acceleration of ions as heavy as uranium.4 The Chemistry of Superheavy Elements reactions using e. The shutdown of this accelerator in 1992 led to a revival of heavy element experiments at the 88-inch cyclotron. This demands a continuous development of ion sources in order to deliver high currents at high ionic charge states. the first accelerators used for the production of heavy elements were the cyclotrons in Berkeley. The principle of separation and detection techniques used in the other laboratories is comparable. was built. Historically. These were the U300 and U400. The developments in the laboratories in Berkeley.g. as used in He-jet systems or mass separators. As a prime example for such instruments. which were developed at the UNILAC. An efficient target cooling and chemical compounds with higher melting points are presently tested. 2. Spatial separation from the projectiles and other reaction products is achieved by combined electric and magnetic fields. increasing beam currents are needed from the accelerators. and also in Finland. Dubna. during the years 1969-74. where ion sources are utilized. in turn. A further improvement of the physical methods was obtained with the development of recoil separators and large area position sensitive detectors. In contrast to the recoil-stopping methods. and later in Dubna. In Berkeley a linear accelerator HILAC (Heavy Ion Linear Accelerator). recoil-separation techniques use the ionic charge and momentum of the recoiling fusion product obtained in the reaction process. The . 300 and 400 centimeter diameter cyclotrons. demand a higher resistance of the targets. Larger and more powerful cyclotrons were built in Dubna for the investigation of reactions using projectiles near calcium. California.2 RECOIL-SEPARATION TECHNIQUES AND DETECTORS The identification of the first transuranium elements was by chemical means. They were only able to accelerate light ions up to about neon with sufficient intensity and up to an energy high enough for fusion reactions. lead or uranium as projectile are possible and may have technical advantages in specific cases. we will describe the velocity filter SHIP (Separator for Heavy-Ion reaction Products) and its detector system. Russia.

helium is used in order to obtain a maximum difference in the rigidities of slow reaction products and fast projectiles. (2) Wien-filter or energy separators use the specific kinematic properties of the fusion products. with half-lives ranging from micro­ seconds to days. It is achieved by additional magnetic fields or symmetric arrangements of electric fields. The detector type to be selected depends on the particle rate. decay mode. then the particles can be implanted directly into the silicon detectors.1. . Two types of recoil separator have been developed: (1) The gas-filled separators use the different magnetic rigidities of the recoils and projectiles traveling through a low pressure (about 1 mbar) gasfilled volume in a magnetic dipole field [16]. A mean charge state of the ions is achieved by frequent collisions with the atoms of the gas. Using position-sensitive detectors. Recoil separators are designed to filter out those nuclei with a high transmission. Ionic-charge achromaticity is essential for high transmission. emitted a particles or fission products. the detectors act as diagnostic elements to optimize and control the ion optical properties of the separator. Recording the data event by event allows for the analysis of delayed coincidences with variable position and time windows for the identification of the decay chains [14]. They are typically in the range of 1-2 microseconds. and half-life. electron capture or fission. one can measure the local distribution of the implanted particles. the positions measured for the implantation and all subsequent decay processes are the same. In general. and detector resolution. Therefore silicon semiconductor detectors are well suited for the identification of nuclei and for the measurement of their decay properties. The latter are created with velocities and energies different from the projectiles and other reaction products. Given that the implanted nuclei are radioactive. An example of such a separator used in experiments for the investigation of heavy elements is the velocity filter SHIP in Darmstadt [13] shown in Figure 1. which are produced in fusion reactions. Properties and Syntheses of Superheavy Elements 5 separation times are determined by the recoil velocities and the lengths of the separators. If the total rate of ions striking the focal plane of the separator is low. Their ionic charge state is determined when they escape from a thin solid-state target into vacuum. Since higher overall yields result in increased background levels. Experimental as well as theoretical data on the stability of heavy nuclei show that they decay by emission. In this case. the transmitted particles have to be identified by detector systems. energy. This is the case because the recoil effects are small compared with the range of implanted nuclei.

The detector signals are also used to distinguish implantation from radioactive decays of previously implanted nuclei. Three secondary-electron foil detectors in front of the silicon detectors are used to measure the velocity of the particles [18]. They are mounted 150 mm apart from each other. and germanium detectors [15].6 The Chemistry of Superheavy Elements The presently used detector system is composed of three time-of-flight detectors. This improvement considerably reduces the background during the measuring period of the decay chain and allows for . the beam-off period is prolonged up to the expected measurable end of the decay chain by opening a third time window. A schematic view of the detector arrangement is shown in the focal plane of SHIP in Figure 1. Three detectors are used to increase the detection efficiency. If the desired conditions are fulfilled. After a response time of a subsequent time window of preset duration opens for counting a preset number of particles of the decay chain. A time-of-flight signal and an energy signal from the silicon detector provide the information for switching off the beam after detection of an implanted residue [19]. seven identical 16-strip silicon wafers.

The reaction used was Five decay chains were observed [22] .29].21]. measured after decay of .5 to 11. element 107.8 MeV. and was identified in a recent chemistry experiment [31]. was first synthesized in 1984 using the reaction The identification was based on the observation of three atoms [27].20.33].The next lighter isotope. revealing a complicated decay pattern. This result irradiation of was confirmed later [34]. Additional data were obtained from the decay [24] and the isotope was identified as granddaughter in the of decay chain of [19. Bohrium. The sequence of three time windows is needed because time-of-flight and energy signals alone would trigger the switching off process for the beam too often due to background events in the corresponding windows. 3. was synthesized at a higher beam energy [23]. Meitnerium. element 108.25]. Presently known nuclei are shown in the partial chart of nuclides in Figure 2. and for the decay of a fission branching of 50 % was also measured. 3.1.25] The isotopes and were produced using the hot fusion reaction [26]. This property seems to be common to many odd and odd-odd nuclides in the region of the heavy elements. In the most recent experiment [24] twelve atoms of were measured.30]. Hassium.1 Experimental Results ELEMENTS PRODUCED IN COLD-FUSION REACTIONS In this section. Only one chain was measured in the irradiation of with The measured event was assigned to the even-even isotope [28]. A detailed presentation and discussion of the decay properties of elements 107 to 109 and of elements 110 to 112 was given in previous reviews [15. as could be concluded from the wide range of energies from 10.2 and Chapter 7. was the first new element synthesized at SHIP using the method of in-flight recoil separation and generic correlation of parentdaughter nuclei. we present results dealing with the discovery of elements 107 to 112 using cold fusion reactions based on lead and bismuth targets. element 109. Properties and Syntheses of Superheavy Elements 7 the safe detection of signals from long lived decays. The more neutron-rich isotope was [19. was first observed in the year 1982 in the with by a single chain [32. see again Chapter 7. The isotope was discovered as a link in the decay chain of [19. The results were confirmed in a later work [21. see Subsection 3. These nuclei were identified after chemical separation.

8 The Chemistry of Superheavy Elements .

The heavier isotope was synthesized with a beam of the more neutron-rich isotope [21]. The first is produced at LBNL in the irradiation of with [36]. The experiment was repeated in May 2000 aiming to confirm the [19]. Another three decay chains were measured in a confirmation experiment in October 2000 [19].1. A total of eight chains were measured during an irradiation time of seven days. one more decay chain was observed. but using slightly synthesis of higher beam energy. The irradiation was performed in January-February 1996. which gave hope that the cross sections could decrease less steeply with more neutron-rich projec­ tiles.The main experiment was preceded by a thorough study of the excitation functions for the synthesis of and using beams of and in order to determine the optimum beam energy for the production of element 110.6 pb to 15 pb by increasing the neutron number of the projectile by two. Over a period of 24 days. The measured decay pattern of the first four agreement with the one observed in the first experiment. this expectation was not proven in the case of element 112. Element 112 was investigated at SHIP using the reaction [30]. Both observations need further experimental clarification. reported to be observed at JINR in the The second isotope is irradiation of with after the evaporation of five neutrons [37]. Spontaneous fission of terminates the decay chain. was observed resulting in a cross section of 0. Decay data were obtained for the ground-state and a high spin K isomer. different from the predictions of reaction theories. for which calculations predict spin and parity or The new nuclei and were identified as daughter products after decay. also shown in decays is in Figure 3. Two more isotopes of element 110 have been reported in the literature. Properties and Syntheses of Superheavy Elements 9 Element 110 was discovered in 1994 using the reaction [29]. The even-even nucleus was synthesized using the reaction [38].5 pb. The chain was assigned to the one neutron-emission channel. The data revealed that the maximum cross section for the synthesis of element 108 was shifted to lower excitation energy. The important result for the further production of elements beyond meitnerium was that the cross section was enhanced from 2. shown in the left side of Figure 3. However. During a similar measuring time. . One decay chain. a total of projectiles were collected. Element 111 was synthesized in 1994 using the reaction A total of three chains of the isotope were observed [25].

it was expected from theoretical calculations. The new results on were proven in a recent chemistry experiment [31]. In order to confirm the data obtained in Berkeley. The experiment is described in . A reanalysis of all decay chains measured at SHIP since 1994. a total of 34 decay chains was analyzed. the same reaction was investigated at SHIP in the summer of 1999. however. Using the new BGS (Berkeley Gas-filled Separator) the reaction was investigated. Results from an experiment at the 88-inch cyclotron in Berkeley aiming to synthesize element 118 were published in 1999 [39].10 The Chemistry of Superheavy Elements A new result was the occurrence of fission which ended the second decay chain at A spontaneous-fission branch of this nucleus was not yet known. revealed that the previously published first decay chain of [30] (not shown in Figure 3) and the second of the originally published four chains of [29] were spuriously created. in which this isotope was measured as granddaughter in the decay chain of see the following Subsection and Chapter 7. Details of the results of the reanalysis are given in [19]. From three decay chains consisting of six subsequent a decays a surprisingly high cross section of 2 pb was deduced for the one neutron emission channel.

A second important difference of actinide target based reactions is the synthesis of more n-rich isotopes compared with a cold fusion reaction leading to the same element.2 ELEMENTS PRODUCED IN HOT-FUSION REACTIONS Hot fusion reactions are based on targets made from actinide elements. Properties and Syntheses of Superheavy Elements 11 detail in [15]. up to the synthesis of seaborgium. a gradual change from cold to hot fusion cannot be studied experimentally.20 MeV in reactions with lead targets and at 35 ­ 45 MeV in reactions with actinide targets. which makes enrichment very expensive. Probably the most significant is the excitation energy of the compound nucleus at the lowest beam energies necessary to initiate a fusion reaction. Due to the lack of targets between bismuth and thorium. actinides were irradiated with light-ion beams from accelerators. A comparison of the measured cross section limit for this reaction with predictions from theoretical models is given in Section 5. Actinides served already as targets. the development of an intense beam at low consumption of material in the ion source and high transmission through the .19 % of this isotope. e. which are closer to the region of spherical SHEs and for which also longer half-lives were expected. The argumentation changed again when elements 110 to 112 had been discovered in cold fusion reactions. when neutron capture and subsequent decay were used for the first synthesis of transuranium elements.1. from a target (see below) and from a target. Therefore. A number of differences exist compared with reactions using lead or bismuth targets. which led to the widely used terminology of cold and hot fusion reactions.g. In addition the lowest excitation energies of compound nuclei from fusion with actinide targets are obtained with beams of The experimental difficulty with using a beam is the low natural abundance of only 0. 3. and the cross section limit resulting from the SHIP experiment for the synthesis of element 118 in cold fusion reactions was 1. Later. During a measuring time of 24 days a beam dose of projectiles was collected which was comparable to the Berkeley value of No event chain was detected.0 pb. The Berkeley data were retracted in the summer of 2001 [40] after negative results of a repetition experiment performed in the year 2001 in Berkeley itself and after a reanalysis of the data of the first experiment. The combination of actinide targets with beams as heavy as became promising to study more neutron rich isotopes. which showed that the three reported chains were not in the 1999 data. Values are at 10 . At that time it was already known that cold fusion reactions yield higher cross sections for heavy element production.

which had been built during the 1980s.5 pb was obtained for the two events. At GNS a search for element 114 was started in November-December. The irradiation started in March. The experiments were performed in collaboration between the Flerov Laboratory of Nuclear Reactions. after evaporation of would be produced and would decay by three neutrons. The two events were tentatively assigned to the residue after 3n evaporation.0 pb. 1998. The separators had been upgraded in order to improve the background suppression and detector efficiency. One decay chain was extracted from the data. They were assigned to the nuclide . two from 112 and two from 114 of the and irradiation with are consistent. Two fission events were measured resulting in a cross section of 5. Fission was measured to The again after decay. The chain was claimed to be a candidate for the The measured cross section was 1 pb [47]. At the separator VASSILISSA attempts were undertaken to search for new isotopes of element 112 by irradiation of with ions [45]. However. A target was irradiated for a period of 34 days with a beam. A cross section of 2.31 MeV) and implantations. The experiments were continued in March 1999.43]. FLNR. LLNL. Two of them could be assigned to fission isomers. The experiments at the U400 cyclotron were performed at two different recoil separators. the nuclide emission into the previously investigated Over a period of 21 days. and the Lawrence Livermore National Laboratory. The fission lifetimes are within the limits given by statistical fluctuations. further investigation is needed for an unambiguous assignment. The energy-dispersive electrostatic separator VASSILISSA was equipped with an additional deflection magnet [42. Livermore. It was expected that.12 The Chemistry of Superheavy Elements accelerator was the aim of the work accomplished in Dubna during a period of about two years until 1998 [41]. Both separators were equipped with time-of-flight detectors and with an array of position-sensitive Si detectors in an arrangement similar to the one shown in Figure 1. The reaction was investigated [46]. a total of four fission events were detected. decay of . when the target was changed from low background rate in the focal plane of VASSILISSA makes mimicking by chance coincidences unlikely. The other two fission signals were preceded by signals from particles (one was an escape of 2. The gas-filled separator GNS was tuned for the use of very asymmetric reactions with emphasis on the irradiation of highly radioactive targets [44]. 1998. California. The four events.

The cross section is about 0. were measured during a beam free period. terminating in spon­ period of 3. 1999. The assignment to the 4n channel is likely. An investigation of element 116 was started in June 2000. but differed from the first chain measured in 1998.5 months. after the parent decay was observed.6 pb deduced from a total beam dose of The newly measured chains are of high significance. The two chains were identical within the statistical fluctuations and detector-energy resolution. 2001 [35].1. All three decay chains are plotted in Figure 4. Properties and Syntheses of Superheavy Elements 13 The experiment was repeated in June-October. The first decay chain which was assigned to was measured after 35 days on July 19. but remains subject to further investigation until an unambiguous identification will become . The data reveal internal redundancy. The irradiation was continued. Using a or were expected to be target. During a sequences. making an origin by chance events extremely unlikely. In particular.5 pb. The beam was switched off using as a trigger the time-offlight and energy signals from the implantation and the decay from the parent. The two new events were assigned to the decay of the 4n evaporation channel. two more taneous fission. because all further decays in the chain. and the lifetimes are relatively short. were observed [48]. the previously detected isotopes observed as daughter products from the decay of the corresponding element 116 parent nuclei produced after evaporation of 3 or 4 neutrons. The cross section was 0. 2000 [49]. and two more decay chains were measured on May 2 and 8.

How well chemical properties can be used for the separation and identification of even single atoms was recently demonstrated in an experiment to study hassium [31]. Similar to the decays and time experiments with recoil separators characteristic chains are used to identify these nuclides in specific correlated fractions or at characteristic positions after chemical separation. like osmium which also forms a volatile tetroxide. Other possible procedures which could help to establish a unique assignment could be measurements of excitation functions.51-54]. direct mass measurements and chemical analysis of parent or daughter elements. to group 8 and thus to element 108 in the Periodic Table of the Elements. generic relations to known nuclei cannot be used. all chemical separations even less for are performed with single atoms on an "atom-at-a-time" scale. The measured decay properties of the separated atoms fully confirmed the data obtained from the decay [19]. As the chains end at by spontaneous fission. Therefore. Using the hot fusion the isotope was produced after reaction evaporation of five neutrons. . Cross sections vary from about 10 nb to a few pb [26. a total of three decay chains were measured reacted with oxygen to form the volatile compound This way it was proven independently by chemical means that the produced atom belongs. With typical beam intensities of ions per second on targets of about thickness production yields range from a few atoms per minute for rutherfordium and dubnium isotopes to five atoms per hour for and and heavier nuclides. Hot fusion reactions applied to synthesize long-lived nuclides of elements 104 through 108 for chemical studies are summarized in Table 1 [50]. see Chapter 7.14 The Chemistry of Superheavy Elements possible. further cross bombardments. The hassium atoms.31.

HFB. They predict for spherical nuclei shells at Z = 114. see Figure 5c. An experimental signature for the shellcorrection energy is obtained by subtracting a calculated smooth macro­ scopic part from the measured total binding energy. Two equally deep minima are obtained.57]. because in the region of SHEs the height of the fission barrier is mainly determined by the ground-state shell correction energy. Partial half-lives decrease almost monotonically from s down to s near Z = 126.1. Properties and Syntheses of Superheavy Elements 4. however. . This way more accurate values for the binding energy are obtained than in the cases of using only the liquid drop model or the shell model. Different results are obtained from self-consistent Hartree-Fock-Bogoliubov.and thus increased stability. The shell-correction energy is plotted in Figure 5a using data from Reference [55]. Nuclear Structure and Decay Properties 15 The calculation of the ground-state binding energy provides the basic step to determine the stability of SHEs. is not sufficient for the calculation of partial spontaneous fission half-lives. The most accurate data were obtained for even-even nuclei using a macroscopic-microscopic model [58]. Nevertheless we see a significant increase of spontaneous fission half-life from s for deformed nuclei to s for spherical SHEs. The valley of nuclei passes through Z = 114. This difference originates from an increasing width of the fission barrier which becomes wider in the case of spherical nuclei. At a distance of about 20 neutrons away from the bottom of this valley. one at Z = 108 and N = 162 for deformed nuclei with deformation parameters and the other one at Z = 114 and N = 184 for spherical SHEs. The knowledge of ground-state binding energies. The shell correction energies of the ground-state of nuclei near closed shells are negative which results in further decreased values of the negative binding energy from the liquid drop model . In macroscopic-microscopic models the binding energy is calculated as sum of a predominating macroscopic part (derived from the liquid-drop model of the atomic nucleus) and a microscopic part (derived from the nuclear shell model). Here it is necessary to determine the size of the fission barrier over a wide range of deformation. N = 184. The landscape of fission half-lives reflects the landscape of shell-correction energies. calculations and relativistic mean-field models [56. half-lives of isotopes have dropped down to values of one second [59]. 120 or 126 (dashed lines in Figure 5a) and N = 184 or 172. while the contribution from the macroscopic liquid-drop part approaches zero for Z = 104 and beyond. Partial spontaneous fission half-lives are plotted in Figure 5b.

16 The Chemistry of Superheavy Elements .

The two regions of deformed heavy nuclei near N = 162 and spherical SHEs merge and form a region of emitters surrounded by spontaneously fissioning nuclei. E. the decay chains end by spontaneous fission at . The four member chain of the heaviest even-even nucleus.6 s . The experimentally observed half-lives.g. are also drawn in the figure. The longest half-lives are 1000 s for deformed heavy nuclei and 30 y for spherical SHEs. decay becomes the dominant decay mode beyond element 110 with continuously decreasing half-lives. Properties and Syntheses of Superheavy Elements 17 Combining results from the individual decay modes one obtains the dominating partial half-life as shown in Figure 6 for even-even nuclei. are 53 ms . observed in the recent experiment in Dubna [35]. and respectively. This is a result of continuously increasing increasing atomic number. is also drawn in Figure 6. For nuclei at N = 184 and Z < 110 half-lives are determined by decay.. The arrows follow approximately the 1-s contour line down to This is in agreement with the experimental observation.1. see Section 3. However. In these cases nuclei. It is interesting to note that the longest half-lives are not reached for the doubly magic nucleus but for Z = values with 110 and N = 182. this deviation is well within the accuracy limits of the calculation.7. Therefore.2. The decay chains of two other recently synthesized even-even [38] and [31]. The nucleus is predicted to decay by spontaneous fission.45 s . respectively. a change of the a energy of by 350 keV only changes the half-life by a factor of 10.6 s.2. which on average is by a factor of 10 longer than the calculated values.

For odd and odd-odd nuclei. the knowledge of the location of minimal negative shell-correction energy is highly important. even-even nuclei portray the situation at high-tide and odd nuclei at lowtide. In the allegorical representation where the stability of SHEs is seen as an island in a sea of instability. All regions for these SHEs are dominated by decay. In that case a wider region of less deep shell-correction energy would exist with corresponding modification of stability and production yield of SHEs. . with respect to an efficient production yield. different concerning the production cross section. half-lives will only be modified by a factor of up to approximately 100. see Chapter 8. when the island is connected to the mainland. Sobiczewski [55] have to be multiplied by a factor of 10 and 1000. partial and spontaneous fission half-lives calculated by R. The survival probability of the compound nucleus (CN) is determined among other factors significantly by the fission-barrier. the uncertainty related to the location of nuclei with the strongest shell-effects. Nuclear Reactions The main features which determine the fusion process of heavy ions are (1) the fusion barrier and the related beam energy and excitation energy. the fission hindrance factors from both the odd proton and the odd neutron are multiplied.18 The Chemistry of Superheavy Elements For odd nuclei. we have to keep in mind that fission hindrance factors show a wide distribution from to which is mainly a result of the specific levels occupied by the odd nucleon. if and to which extent uncertainties related to the location of proton and neutron shell closures will change the half-lives of SHEs. the island character of emitters prevails disappears and for nuclei with neutron numbers 150 to 160 down to rutherfordium and beyond. The line of reasoning is. 5. For odd-odd nuclei. Smolanczuk and A. The interesting question arises. respectively. it may also turn out that shell effects in the region of SHEs are distributed across a number of subshell closures. However. Therefore. However. Partial and half-lives are only insignificantly modified by shell effects. This is different for fission half-lives which are primarily determined by shell effects. if the double shell closure is not located at Z = 114 and N = 184. However. thus making provisions for the odd particle hindrance factors. and thus longest partial fission half-life at Z = 114. because their decay process occurs between neighboring nuclei. however. is irrelevant concerning the longest 'total' half-life of SHEs. 120 or 126 and N = 172 or 184.

The decrease is explained as a combined effect of increasing probability for reseparation of projectile and target nucleus and fission of the compound nucleus.5 pb. see e. Considering the already long irradiation time to reach a cross section of 0.62]. because it is solely built up from shell effects.1. (2) The cross sections for elements lighter than 113 decrease by factors of 4 and 10 per element in the case of cold and hot fusion. Note in this context that the experimental sensitivity increased by three orders of magnitude since the 1984 search experiment for element 116 using a hot fusion reaction [60]. The effect of Coulomb repulsion on the cross section starts to act severely for fusion reactions to produce elements beyond fermium. respectively. respectively. The experimental time necessary to observe one decay chain at a certain cross section is given on the right ordinate of Figure 7a. From there on a continuous decrease of cross section was measured from microbarns for the synthesis of nobelium down to picobarns for the synthesis of element 112. In fusion reactions towards SHEs the product reaches extremely large values and the fission barrier extremely small values. the fission barrier itself is fragile. suggest that the steep fall of cross sections for cold fusion reactions . Data obtained in reactions with and for the In-evaporation channel at low excitation energies of about 10-15 MeV (therefore named cold fusion) and in reactions with actinide targets at excitation energies of 35-45 MeV (hot fusion) for the 4n channel are plotted in Figure 7a and b. Properties and Syntheses of Superheavy Elements 19 (2) the ratio of surface tension versus Coulomb repulsion which determines the fusion probability and which strongly depends on the asymmetry of the reaction partners (the product at fixed (3) the impact parameter (centrality of collision) and related angular momentum.g.5 pb. For these reasons the fusion of SHEs is hampered twofold: (i) in the entrance channel by a high probability for reseparation and (ii) in the exit channel by a high probability for fission. This is the limit presently set by experimental constraints. [61. In addition. the fusion of lighter elements proceeds unhindered through the contracting effect of the surface tension and the evaporation of neutrons instead of fission. and (4) the ratio of neutron evaporation and of emission versus the fission of the compound nucleus. Some features which the data reveal are pointed out in the following: (1) So far no data were measured below cross section values of about 0. In contrast. Theoretical consideration and empirical descriptions. Further improvement of the experimental conditions is mandatory. it seems impractical to perform systematic studies on this cross section level or even below.

The relatively high values measured in Dubna for the synthesis of elements 114 and 116 would be in agreement with this argumentation. However. . strong shell effects for SHEs with spherical nuclear shapes could lead to an increase of the fission barrier and thus to an increase of the survival probability of the compound nucleus. Extremely small values result from an extrapolating these data into the region of element 114 and above. In the case of cold fusion only cross section limits are known for the synthesis of elements 116 and 118.20 The Chemistry of Superheavy Elements may be strongly linked to increasing reseparation probability at high values of while hot fusion cross sections mainly drop because of strong fission losses at high excitation energies. see also discussion in Section 4.

sometimes also called "warm" fusion process. The reason is not only a low reaction Q-value and thus low excitation energy. In this view the difference between cold and hot fusion is not only a result from gradually different values of excitation energy. was performed at a beam energy resulting in an excitation energy of approximately 34 MeV [35]. the assumption could not be confirmed in the case of element 112 which was synthesized using the most neutron rich stable zinc isotope with mass number 70. Target nuclei of actinide targets are strongly deformed and the height of the Coulomb barrier depends on the orientation of the deformation axes.1. A number of excitation functions was measured for the synthesis of elements from No to 110 using Pb and Bi targets [15]. where the reaction partners maintain kinetic energy up to the closest possible distance. possibly along a fusion valley less pronounced than in the case of cold fusion. An excitation function which could provide experimental evidence for an orientation effect on the fusion cross section is not yet measured. but also that fusion of such systems is connected with a minimum of energy dissipation. The maximum evaporation residue cross section (1n channel) was measured at beam energies well below a one dimensional fusion barrier [63]. At the optimum beam energy projectile and target are just reaching the contact configuration in a central collision. which is on the one hand (cold fusion) based on a well ordered fusion process along paths of minimum dissipation of energy. and are discussed in the literature. The fusion path proceeds along cold fusion valleys.67-72]. a number of theoretical studies are in progress aiming to obtain a detailed understanding of the processes involved [65. However. The observed decay chains were assigned to the 4n-evaporation channel.65]. and on the other hand (hot fusion) based on a process governed by the formation of a more or less energy equilibrated compound nucleus. Properties and Syntheses of Superheavy Elements 21 (3) Locally an increase of the cross section by a factor of 5. Fusion of the doubly magic and actinide targets seems to proceed via an intermediate. . Among these processes transfer of nucleons and an excitation of vibrational degrees of freedom are the most important [64. but there exists a qualitative difference. Triggered by the recent experimental success of heavy element synthesis. The relatively simple fusion barrier based on the Bass model [63] is too high and a tunneling process through this barrier cannot explain the measured cross section. Various processes are possible. It was pointed out in the literature [66] that closed shell projectile and target nuclei are favorable synthesizing SHEs. The reaction studied in Dubna. which result in a lowering of the fusion barrier.8 was measured for element 110 in cold fusion reactions when the beam was changed from to It was speculated that this increase could be due to the increased value of the projectile isospin.

these measurements can be complemented by in-beam spectroscopy using the recoil-decay tagging method in order to study the influence of angular momentum on the fusion and survival probability [73-75]. more data will be measured in order to promote a better understanding of the stability of the heaviest elements and the processes that lead to fusion. New developments will not only make it possible to perform experiments aimed at synthesizing new elements in reasonable measuring times. information about the 'shape' of the fission and the fusion barriers can be obtained. The progress towards the exploration of the island of spherical SHEs is difficult to predict.22 The Chemistry of Superheavy Elements Due to the great uncertainty concerning the influence of the various steps in the fusion of heavy elements. recent data on the synthesis of element 114 and 116 in Dubna using hot fusion seem to break this trend when the region of spherical superheavy elements is reached. However. and that ex­ citation functions are measured. A microscopic description of the fusion process will be needed for an effective explanation of all measured phenomena in the case of low dissipative energies. From both slopes. One can hope that. Therefore a confirmation is urgently needed that the region of spherical SHEs has finally been reached and that the exploration of the 'island' has started and can be performed even on a relatively high cross section level. An opportunity for the continuation of experiments in the region of SHEs at decreasing cross sections afford. Then. 6. among others. many questions of more general character are still awaiting an answer. It is especially important that various combinations of projectile and target be investigated. from very asymmetric systems to symmetric ones. more precise experimental data are needed. despite the exciting new results. during the coming years. but will also allow for a number of various other investigations covering reaction physics and spectroscopy. Summary and Outlook The experimental work of the last two decades has shown that cross sections for the synthesis of the heaviest elements decrease almost continuously. At a high enough cross section. the relationships between fusion probability and stability of the fusion products may also become apparent. However. High current beams and radioactive beams are options for the . further accelerator developments. and how fast cross section decrease on the low energy side due to the fusion barrier. This provides information on how fast cross section decrease with increasing energy due to the fission of compound nuclei.

the cross section level for the performance of experiments can be shifted down into the region of tens of femtobarns. not as intense as the ones with stable isotopes. Based on nuclear models. Interesting will be the study of the fusion process using radioactive neutron rich beams. Radioactive ion beams. At increased beam currents. . call for the development of new targets and separator improvements. The half-lives of spherical SHEs are expected to be relatively long. values from microseconds to years have been calculated for various isotopes. in turn. Properties and Syntheses of Superheavy Elements 23 future. will allow for approaching the closed neutron shell N = 184 already at lighter elements.1. High currents. values of tens of particle may become accessible. from the safe identification of short lived isotopes by recoilseparation techniques to atomic physics experiments on trapped ions. and excitation functions can be measured on the level of tenths of picobarns. which are effective predictors of half-lives in the region of the heaviest elements. This wide range of half-lives encourages the application of a wide variety of experimental methods in the investigation of SHEs. and to the investigation of chemical properties of SHEs using long-lived isotopes.

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20 Element 118 1 Maximum number Experimental techniques 11 Abundance Accelerators 4 5 Background Beam currents 4. 20 Shell-correction energies 15. 20 12 Fission isomers Ground-state binding energy 15 Half-lives 23 High spin K isomer 9 18 Hindrance factors Magic numbers 2 18 Odd nuclei Odd-odd nuclei 18 16. 9. 12 6 Germanium detectors Identification 5 In-beam spectroscopy 22 Irradiation time 19 Mass measurement 14 Position-sensitive detectors 5. 17. 14. 17 Spontaneous fission 1. 10. 22 14 Chemical analysis 5. 21 Element 110 9 Element 111 9. 18 Partial half-lives Shell effects 18. 4. 17 decay 17 15 stable nuclei .28 The Chemistry of Superheavy Elements Index Elements 7 Element 107. 15 Liquid-drop model Macroscopic-microscopic 15 model Relativistic mean-field model 15 15 Self-consistent model 2. 13. 23 Targets Time-of-flight detectors 6. hassium 7 Element 109. 15 Shell model Nuclear properties Atomic masses 2 Chart of nuclides 7 2. 21 Element 112 20 Element 114 13. 16.6 Velocity separator Nuclear models 1. 12 22 Radioactive beams 12 Radioactive targets 4. 15. 10. 18 Subshell closure 18 Total half-life 18 decay 16 chains 8. 11. 18 Spherical nuclei 15. 6. 20 Element 116 10. 13 6 Target wheel 3. 17 Deformed nuclei 2 Doubly magic nuclei 17 Electron capture 17 Even-even nuclei Fission barriers 15. 14 Correlation method 14 Cross bombardments 4 Detectors 12 Electrostatic separator 11 Enrichment 14 Excitation functions Gas-filled separator 5. meitnerium 9. 15. 19. 14. 12 5 Transmission 5. 9. bohrium 7. 12. 23 Recoil separators 22 Recoil-decay tagging 5 Separation time Switching off the beam 6. 14 Element 108. 21 Closed shells Deformation parameters 15 15.

1. 17 2 2 18 15 . 14. Properties and Syntheses of Superheavy Elements Nuclear reactions 1n evaporation channel 19. 22. 20. 18 Production yield 19 Reseparation 19 Surface tension 20 Survival probability 22 Symmetric systems 21 Transfer of nucleons Vibrations 21 Superheavy elements Island of stability Location Occurance in Nature Production yield Sea of instability Shape 18 2. 18 Compound nucleus 21 Contact configuration 19 Cross section limits 21 Energy dissipation 19 Entrance channel 11. 3. 20. 21 4n evaporation channel 13. 18. Excitation energy 21 Excitation functions 3. 19. 21 Impact parameter 19 3 Inverse reactions 19 Neutron evaporation 11 n-rich isotopes 21 Nuclear orientation Production cross section See Production yield 14. 23 19 Exit channel Fission of compound nucleus 19. 21. 21. 19. 19 Beam energy 21 Central collision 7. 21 Cold fusion 2. 22 18. 19. 20 22 Angular momentum 22 Asymmetric systems 21 Bass model 18. 11. 18 29 Fusion valleys 21 Hot fusion 11. 22 Fusion barrier Fusion reaction 3.

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31-94 © 2003 Kluwer Academic Publishers. Printed in the Netherland . Germany 1. Darmstadt [1-3] and some decay chains and fission products associated with production of even more heavy elements 116 and 114 were recently reported by the Joint Institute for Nuclear Research (JINR). D-64221 Darmstadt. information on its chemical behavior is often used to place an element in a chemical group. 1. This period of time was also very fruitful with studying chemical properties of the very heavy elements [5-9]. Pershina Gesellschaft für Schwerionenforschung mbH. Schädel (ed. some fast chemistry techniques are used. with increasing nuclear charge the cross sections and the production rates drop so rapidly that such chemical information can be accessed only for elements with a half-life of the order of at least few seconds and longer. Since they cannot be measured for the very heavy elements. They are based on the principle of chromatographic separations either in the gas phase exploiting the differences in volatility of heavy element compounds.).Chapter 2 Theoretical Chemistry of the Heaviest Elements V. Dubna [4]. or in the aqueous 31 M. Conceptually. In this case. it is the atomic number and the electronic configuration of an element that define its position in the Periodic Table. The Chemistry of Superheavy Elements. Introduction The last decade was marked with the discovery of five new members of the Periodic Table: The heaviest elements of the last transition element series 110 through 112 were identified in the Gesellschaft für Schwerionen­ forschung (GSI). Unfortunately. Planckstr.

for the heaviest elements. theoretical predictions of experimentally studied properties are especially valuable in order to help design the required sophisticated and expensive experiments with single atoms. For heavy elements. These improvements. caused a boom in the molecular relativistic electronic structure studies of the heaviest elements as the number of publications in Figure 1 shows. It mostly answers the question about whether a new element behaves similarly or differently than its lighter congeners in the chromatographic separation processes: Due to very strong relativistic effects on the valence electronic shells of the heaviest elements. is mandatory [12-14]. Due to the very short half-lives. Presently. along with the motivating experimental results. Moreover. Special attention is paid to the predictive power of the theoretical studies for the chemical experiments. cannot be measured at all. Some first results were reported on gas-phase chemical experiments with element 112 [11]. chemical information obtained from these experiments is limited to the knowledge of only a very few properties. and resulted in some remarkable achievements. electron affinities (EA). some important spectroscopic properties like ionization potentials (IP). some deviations from trends known for the lighter homologues in the chemical groups are expected. and molecular and atomic programs based on it. Problems and challenges of the theoretical . Chemistry of elements 104 through 108 has been successfully studied using these techniques [5-10]. Thus. The present publication is an overview of the results of the recent theoretical investigations in the area of the heaviest elements (Z=103 and higher) and it provides their comparative analysis. Density Functional Theory methods were improved with respect to the treatment of non-local (exchange-correlation) effects [18] and the ab initio Dirac-Fock theory has advanced due to the development of basis set techniques and treatment of electron correlation [19]. theoretical studies become extremely important and are often the only source of useful chemical information. It has been shown [15-17] that even trends in properties can be predicted erroneously by using non-relativistic approximations. Simple extrapolations of properties from those of the lighter elements are also unreliable and can lead to erroneous predictions. the use of the relativistic quantum theory. Relativistic quantum theory and quantum-chemical methods have been tremendously developed in the last two decades to accurately treat both relativistic and correlation effects for the many-electron problem. The chemical composition of heavy element compounds cannot be experimentally established either and can only be assumed by comparing their behavior with those of lighter congeners. force constants etc.32 The Chemistry of Superheavy Elements phase by solvent extraction or ion exchange separations using differences in the complex formation (see the related chapters in this book).

That was possible due to the development of very accurate relativistic quantum chemical methods and programs. see reviews [31. Architecture of the Periodic Table When G. the filled-shell concept was in accord with the newly found periodicity in chemical properties and resulted in the discovery of all the heavy actinides at that time [20]. J. the theory advanced to such an extent that the Periodic Table. which could reliably calculate electronic configurations of heavy element atoms and ions.T. Greiner [22] and J. The results up to 1975 are summarized in the review of B. B. W. Waber. Fricke. Theoretical Chemistry of the Heaviest Elements 33 research in this area related to the necessity of improving the used techniques and obtaining the desired chemical information are described.2. Seaborg in 1944 introduced his ‘actinide’ concept the theory played not the last role in his decision to place newly discovered elements in a second series where the filling of the 5f-shell takes place. Since then. More accurate multiconfiguration Dirac-Fock (MCDF) [24-30] and coupled cluster (CC) calculations. see [12] and references therein. Thus. Mann [21]. Ground states for the superheavy elements up to Z = 174 were predicted in the late sixties and early seventies by J. Fricke.B. see Figure 2. T. Desclaux [23] using the Dirac-Fock (DF) and DiracFock-Slater (DFS) methods. .P. is now predicted with sufficient accuracy up to very high Z numbers. 2. performed in the eighties and nineties basically confirmed those earlier predictions and furnished more reliable values of the electronic energy states.32]. similarly to the ‘lanthanide’ series where the filling of the 4f-shell takes place.

the situation becomes more complicated: 7d. Followed by them are the 7p elements 113 through 118. however.34 The Chemistry of Superheavy Elements According to results of these calculations. Z=122. The next element. has a relativistically stabilized 8p electron in its ground state electronic configuration in contrast to what would be predicted by a simple extrapolation in the group. Its structure cannot be understood without knowledge of the . that without relativistic effects. f and g blocks are not distinguishable any more. the chemistry of the heaviest superheavy elements would also be different to that of their lighter homologues due to very large shell structure effects. see the Periodic Table till Z=173 in [12]. so that these elements will obviously be homologues of alkali elements in groups 1 and 2. the filling of the 8s shell takes place. 121. d. and levels are located energetically so close to and further on 9s. 6f and 5g levels. The clear structures of the pure p. It is interesting to note. The modern Periodic Table up to element 153 is shown in Figure 2. a 7d electron is added to the ground state. This is the last element where accurate calculations [33] exist. Beyond element 122. In the next element. in the first nine of the transactinide elements (Z = 104 to 112) the filling of the 6d shell takes place. Chemical properties of these elements influenced by all these mixed electronic shells will then be also so different to anything known before that any classification just of the basis of their knowledge will be impossible. In elements 119 and 120. with element 118 falling into the group of noble gases. each other that in the Z = 160 region the usual classification on the basis of a simple electronic configuration may become invalid. so that it is in contrast to the state of Th.

. shown that the direct relativistic stabilization is still large for the outer s and valence orbitals. however. e. (The 1s electron of Sg.g. The contraction of the outer s and orbitals was recently explained as due to the admixing of higher bound and (partially) continuum orbitals due to relativistic perturbations [34]. which will be considered in the following section.g. 3. is 25% relativistically contracted. The effective decreases. Db. The contraction and stabilization of the s and orbitals is known to be the direct relativistic effect and it was shown to originate from the inner K and L shells region [34]. . where see Figure 3. has so that its radius shrinkage is 37%). for a hydrogen-like s and electrons. as a consequence. 7s orbital for element 105. Theoretical Chemistry of the Heaviest Elements 35 influence of relativistic effects on the electronic shells. It was.2. Thus. Relativistic and QED Effects on the Orbital Shells With increasing Z of heavy elements causing a stronger attraction to the core an electron is moving faster. This effect was originally thought to be large only for the “fast” electrons in inner core shells of heavy atoms. e. so that its mass increase is where is the rest mass and Bohr radius is the velocity of the electron..

It should be realized that though contracted s and core (innermore) orbitals cause indirect destabilization of the outer orbitals. . the indirect relativistic effect is influenced by the outer core orbitals. The shift of the maximum to element 112 in the row in contrast to gold in the row is due to the fact that in both the 111 and 112 elements the ground state electronic configuration is while the electronic configuration changes from to The second (indirect) relativistic effect is the expansion of outer d and f orbitals: The relativistic contraction of the s and shells results in a more efficient screening of the nuclear charge. While the direct relativistic effect originates in the immediate vicinity of the nucleus. the phenomenon on Au (17. see Figure 4. respectively. The same maximum is. consequently. That partially explains the very large relativistic stabilization of the 6s and 7s orbitals in Au and element 112.36 The Chemistry of Superheavy Elements The effect of the ns orbital contraction reaches its maximum in the row row on element 112 (31%). observed with the relativistic stabilization of the 6s and 7s orbitals. relativistically expanded d and f orbitals cause the indirect stabilization of the valence s and p-orbitals. respectively: Since d shells (it is also valid for the f shells) become fully populated at the end of the nd series.3%) and in the being called the relativistic effects gold maximum and group 12 maximum. there will occur a maximum of the indirect stabilization of the valence s and p orbitals [34]. so that the outer orbitals which never come to the core become more expanded and energetically destabilized.

2. i. in size compared to typical bond energies.g. the non-relativistic description of the wave function would still give the right trend in properties from the 4d to the 5d elements. i. as well as the destabilization of the (n-1)d orbitals for group-8 elements.. f.8 eV. The third relativistic effect is the well-known spin-orbit (SO) splitting of levels with l > 0 (p. Thus.e. see Figure 6.. . d. In transactinide compounds SO coupling becomes similar. while it would result in the opposite and consequently wrong trend from the 5d to the 6d elements. The SO splitting decreases with increasing l for the same principal quantum number. The SO splitting of the valence 7p electrons in element 118. e. The SO splitting for the same l decreases with increasing number of subshells. One can see that trends in the relativistic and non-relativistic energies of the valence electrons are opposite from the 5d to the 6d elements.. electrons) into j = l ± ½. All the three relativistic effects are of the same order of magnitude and they grow roughly as . or even larger. is as large as 11. It also originates from the inner region in the vicinity of nucleus.e.. the splitting is larger than the and both are larger than the It is explained by the orbital densities in the vicinity of nucleus decreasing with increasing l.. it is much stronger for inner (core) shells than for outer shells. Theoretical Chemistry of the Heaviest Elements 37 Figure 5 demonstrates the relativistic stabilization of the ns orbitals. as an example.

In element 121. 0.6 % in splitting and are of the order of correlation effects there [14].g. while for (n-1)d electron is an indirect stabilization. and nuclear volume contributions to it for coinage metals at the DF level is shown in Figure 7.38 The Chemistry of Superheavy Elements Breit effects (accounting for magnetostatic interaction) on energies of the valence orbitals and on IP are usually small. they are of about 0..g. e. reach few % for the fine structure level splitting. 3. Breit. For highly charged few electron atoms they were found to approach the Breit correction to the electron-electron interaction [36]. e.. They can. however.1 eV for transition energies between the states including f orbitals [35]..02 eV for element 121 [35]. The quantum electrodynamic (QED) effects are known to be very important for inner-shells. The nuclear volume effects grow even faster . in accurate calculations of X-ray spectra. The result for the valence ns electron is a destabilization.g. e. Comparison of the valence ns Lamb shift (the vacuum polarization and selfenergy) with the ns valence orbital energy and the relativistic. In the middle range (Z = 30–80) both the valence-shell Breit and the Lamb-shift terms behave similarly to the kinetic relativistic effects scaling as For the highest Z values the increase is faster. Similar effects were also found for valence ns electrons of neutral alkali-metal and coinage metal atoms [37].

be only shortly described here with the accent put on those which were used for calculations of the transactinide systems. They were overviewed in application to transition elements [13]. 4.1 AB INITIO SOLUTION OF THE DIRAC EQUATION The Dirac-Coulomb-Breit (DCB) Hamiltonian is a satisfactory starting point for calculations of many-electron systems in the sense that it treats electrons relativistically and the most important part of . which means that the existing studies of relativistic effects are up to 99% correct [37]. and transactinides [15-17]. 4. They will. Relativistic Quantum Chemical Methods for Atoms and Molecules Methods to calculate the electronic structures of very heavy element compounds are the same relativistic methods which can be applied to any relativistic systems. actinides [38].2. the results show that valence ns-shell Lamb shifts are not negligible: They are of the order of 1-2% of the kinetic relativistic effects. Theoretical Chemistry of the Heaviest Elements 39 with Z. Thus. therefore.

The DCB Hamiltonian (Equation 3) accounts for the correlation effects in the first order via the term.21-23].P. and the electron Dirac Hamiltonian operator for the instantaneous Coulomb interactions between electrons is the Breit term The includes the effect of the finite nuclear size. like QED.40 The Chemistry of Superheavy Elements the electron-electron interaction nonperturbatively. It can treat a large number of open shell configurations and can be applied to elements with any number of valence electrons. called electron correlation. the MCDF method based on the CI technique was used. The latter is of the order of magnitude of relativistic effects and may contribute to a very large extent to the binding energy and other properties. the “no-pair“ Hamiltonian [40] is restricted then to contributions from the positive-energy spectrum and puts Coulomb and Breit interactions on the same footing in the SCF calculations. Since the Dirac equation is written for one electron. 4.1 Atomic codes Earlier predictions of chemical properties of the heaviest elements were made on the basis of atomic single-configuration DF and DS calculations using approximations of eqs. projection one. (3-5) and numerical techniques [12. Grant [30. There are several modifications of this method: the codes of J. Since the relativistic many-body Hamiltonian cannot be expressed in closed potential form. which means it is unbound.and two-electron operators are used to solve this problem [39]. Calculations of IPs of the heaviest elements from Lr through element 108 [24-29] and elements 113 through 117 [30] were performed . The advantage of this method is that it accounts for most of the correlation effects while retaining relatively small number of configurations. FröseFisher [43]. It contains the oneincluding the nuclear potential. while some finer effect. can be added to the perturbatively. Desclaux [42]. the many-body perturbation theory (MBPT) and by the presently most accurate coupled cluster (CC) technique. In this form. The DCB Hamiltonian in this form contains all effects through the second order in the fine-structure constant.P.41] and S. Some higher order of magnitude correlation effects are taken into account by the configuration interaction (CI). Later.1. I. The operator projects onto the space spanned by the positive-energy spectrum of the Dirac-Fock-Coulomb (DFC) operator. the real problem of ab initio methods for a many-electron system is an accurate treatment of the instantaneous electron-electron interaction.

since it takes into account most of dynamic correlation effects.g. Kaldor and I. Equation 3. with an average error of 0. particle valence sectors of the Fock space. Equation 3. Theoretical Chemistry of the Heaviest Elements 41 using the MCDF method. large basis sets are needed to describe accurately the inner shell region where relativistic pertur-bation operators are dominant. CCSD. Correlation effects are taken into account by action of the excitation operator defined in the Fock-space CC approach with respect to a closed-shell reference determinant. Algebraic solution of the molecular Dirac equation encounters difficulties due to the fact that the Dirac operator is unbound.) Calculations of two-electron integrals require large disk space and computational time.2. since excit­ ations of the type cannot be handled. It is based on the DCB Hamiltonian. An average error for IP is about 1 eV. 4. In addition to the traditional decomposition into terms with different total number of excited electrons (l). and some core polarization. The condition of the kinetic balance should be observed relating the large and small components of the fourcomponent wave-function [41]. e. The method is very accurate. omitted from the MCDF method and a core polarization.32. S is partitioned according to the number of valence particles (m) or holes (n). the method is limited to one or two (single-double excitations. it can. Correlation effects are taken into account by using . it can treat the states which can be reached from a closed shell by adding or removing no more than two electrons.44]. presently not handle the elements of the middle of the 6d series (with the number of 6d electrons more than 2) leaving this area to the MCDF calculations. Presently. i. It was applied to the calculations of electronic energy states of a number of the heaviest elements up to Z = 122 [33]. Due to the mentioned limitation of the method.e. however. Based on them molecular (DF)-LCAO codes inclu-ding correlation effects are still under development [19] and calculations are restricted to molecules with very few atoms.1.2 Molecular ab initio ‘fully’ relativistic methods Molecular fully relativistic ab initio methods use the same DFC or DCB Hamiltonians. (Kinetically balanced Gaussian type wave functions with a Gaussian distribution for the nuclear potential are presently best suited. U. Some special techniques like the projection operator technique are used to avoid connected with it the variational collapse. The limited accuracy of this method is due to omitting dynamic correlations. Another recently created correlated method is the no(virtual)pair DF (DCB) coupled-cluster technique of E. Eliav.1 eV for excitation energies. In contrast to non-relativistic calculations. Ishikawa [31.

a pseudopotential where AREP stands for a spin-averaged or scalar relativistic effective core potential. The RECP have recently been further improved by introducing a special technique (of nonvariational restoration of the electronic structure in the core) to correct an error intro­ duced by a smoothing of the orbitals in the core region (nodeless wavefunction). frozen inner shells are omitted and replaced in the Hamiltonian by an additional term. Such potentials for elements Am through 118 were generated by C. Then.. see Table 1. The cal­ culations are still very sophisticated and expensive. The aim of those calculations was mainly to test relativistic and correlation effects on model systems.42 The Chemistry of Superheavy Elements the same techniques as those of the atomic codes: CI [45] or MBPT (e. The SO splitting is obtained using the effective SO operator. MP2. 4. the CCSD [47]. where T stands for ‘triple’) included. The calculations for the molecules. As a result. which may be essential for dissociation and transition energies (as high as The method is called the generalized RECP. Nash et al. Another type of methods belonging to this group is the energy-adjusted pseudo potentials (PP) which uses atomic spectra (energies) for generating .2 RELATIVISTIC PSEUDO-HAMILTONIANS An efficient way to solve a many-electron problem is to apply relativistic effective core potentials (RECP). The following calculations for heavy and superheavy elements should be mentioned: (DF–KRCCSD) [47].g. and and are the Coulomb and exchange operators. (113)(117) (DF) [49-51] and (DF-MP2) [52]. MP2 [46]) and. Calculations for ground and excited states of HgH [56] show very good agreement with experiment for binding and excitation energies. where experimental data are available. The is usually fitted to one-component or two-component all-electron DF or DHF relativistic atomic wave functions [53]. hence the number of two-electron integrals. GRECP / RCC [55]. CCSD(T). 111H. 117H. the number of basis functions is drastically diminished and. are very promising. the second order Møller-Plesset. recently. the one-electron integrals are solved for the valence basis functions and this additional term by applying ab initio schemes at the SCF level or with electron correlation (CI.S. [54]. (DFC) [48]. According to this approximation.

64]). Thus. and enlarge the binding energy by 0.26 Å (the HF-DF difference without correlation) or by 0. the DFT became extremely useful in the application to large heavy-element molecules. but enhances by 1.DF+MP2 difference with correlation).34 eV. Due to its relative simplicity. so that a SOPP are obtained. relativistic effects diminish the equilibrium bond length by 0. The data of Table 1 demonstrate the importance of relativistic and electron correlation effects. see [18. but the Hamiltonian includes the Darwin and mass-velocity terms and omits the spin-orbit effects. which technically can be too demanding and expensive. Several RECP and PP calculations were performed for gas-phase compounds of the heaviest elements [17].21 Å (the HF+MP2 . The method is implemented in the commercial system “Gaussian 98“. solutions and solids.21 eV (the HF+MP2 . 4. It has extensively been applied to calculations of transitionelement and actinide systems [62]. SO effects can be included in average relativistic (AR)PP calculations by adding a SO operator. a sort of a test molecule (see also [63. non-relativistic.2. correlated and noncorrelated methods in comparison with experimental results is shown in Table 1 for AuH. even for AuH correlation amounts almost to 50% of the chemical bond strength. Systems with the large number of atoms can be treated with sufficient accuracy.3 DENSITY FUNCTIONAL THEORY Density Functional Theory (DFT) is primarily a theory of electronic ground state structure expressed in terms of the electronic density. The advantage of the method is the possibility to calculate quite economically rather large systems.DF+MP2 difference with correlation). clusters.65] and references therein. The latter are then included via the perturbation operator after the wave functions have been obtained. These PP were generated for the transactinides [60]. Correlation on the DF level by 0. diminishes Thus. To achieve a high accuracy. The computing time in the DFT for a system of many atoms grows as or while in traditional methods as The present upper The modern DFT is in principle exact and the accuracy limit is of .07 eV.70 eV (the HF-DF difference without correlation) or by 2. No additivity of correlation and relativistic effects was shown. The quasirelativistic (QR) PP of Hay and Wadt [61] use two-component wave functions. The accuracy of the various relativistic. Theoretical Chemistry of the Heaviest Elements 43 the [57-59]. a large number of correlated states has to be taken into account in the fitting procedure.

The introduction of the RGGA for [66] (Equation 13) and of an accurate integration scheme. (10-13). both quantitatively and conceptually. is the highest level of approximation for the exchange-correlation potential taking into account the non-local effects [66]. .16]. Based on it DFT methods are alternative and functional complementary. the single-particle equations are or the (relativistic) generalized gradient approximation (RGGA). to the traditional methods where the many-electron wave function is used. Another error in introduced by the single-particle approximation could be corrected by using the MCDF method for atomic calculations when calculating dissociation energies [70]. There are several methods based on eqs. Another four-component ‘fully relativistic’ DFT program is the Beijing density functional (BDF) method [71]. where the Slater exchangecorrelation term was used. (R)LDA (the one level below approximation). The so-called ‘fully relativistic’ DFT methods use four-component (numerical or combined with which means that the spin-orbit is some Slater type) wave functions included explicitly from the beginning. The DS-DV method was extensively applied to calculations of various gas-phase and aqueous phase compounds of the transactinides [15. The method is presently used by us for optimization of geometry and binding energy calculations of heavy element compounds.44 The Chemistry of Superheavy Elements depends on the adequate knowledge of the exchange-correlation energy [18]. The results will be discussed in the following chapters. Four-component numerical atomic spinors obtained by finite-difference atomic calculations are used for cores. since it falls off exponentially and not as 1/r. A predecessor of this group of the methods was the intrinsically approximate Dirac Slater discrete variational (DS-DV) method of Ellis and Rosen [67]. The Hamiltonian used here is the same as given in Equation 3 plus an additional exchange-correlation term Thus. This approximation reduces the failure of the (relativistic) local density approximation. the minimization of an error in the total energy by an additional fitting procedure and the use of optimized basis sets have resulted in a drastic reduction of errors in the binding energy calculations [68-70] which was previously a main drawback of the DS-DV method. describing the asymptotic behavior of the exchange and correlation potential in a wrong way.

however. Young [82] should also be mentioned here. Rösch [79. and gives reliable optimization of geometry and bonding. Case and C. known as the Amsterdam (ADF) method [74].2. F.A. Another one-component quasirelativistic scheme [78] applied to the calculations of dimers of elements 111 and 114 [72. however. Ziegler [81]. Br.80].73]. O) were reported [72. I. The basis functions for the elements beyond 103 have. Cl. the spin operator was also included in the ZORA Fock operator [77]. An earlier version of the method used a QR Hamiltonian (Darwin and massThe spin-orbit effects were taken into velocity terms) and the GGA for account by perturbation operators. Recently. The non-relativistic GGA for is used. not yet been generated.4 OTHER METHODS There is quite a number of other theoretical methods appropriate for calculations of the electronic structure of heavy elements with some . Theoretical Chemistry of the Heaviest Elements 45 while basis sets for valence spinors are a combination of numerical atomic spinors and kinetically balances Slater-type functions. like 114. not applied to the heaviest elements. In the modern version of the method the Hamiltonian contains relativistic corrections already in the zeroth-order and is called the zeroth-order regular approximation (ZORA) [76].Y. Calculations of small transactinide systems.73] is a modification of the ZORA method. ZORA can deviate from the 4-component DFT results due to improper description of the spinors [73]. The accuracy of some of the DFT methods for AuH is shown in Table 1. Some other relativistic DFT codes like those of N. T. and of D. 4. For elements with a very large SO splitting. The ZORA method uses analytical basis functions. like 111X and 114X (X = H. One-component quasirelativistic density-functional method extensively used in the calculations of the electronic structure of transition element and actinide compounds. is the successor of the quasirelativistic Hartree-Fock-Slater (QR-HFS) one [75]. They were.

not confirmed by more accurate CCSD calculations [88]. expansion techniques. One should mention here the Douglas-Kroll-Hess (DKH) [84] method. The next excited state. which can be applied if SO effects are small (it was also used for calculations of the electronic structure of 111H [50]). atomic/ionic radii (AR/IR). and from different energies and radial extension of the valence orbitals. 5.9 eV above the state. than the one of Hf This state was shown to be J=2 (80% of with the first excited state (95%) lying 0. For Rf.90].1 ELECTRONIC CONFIGURATIONS Lr was the first element where a strong relativistic stabilization of the electron was supposed to result in an unusual ground state electronic in contrast to The MCDF calculations configuration. Atomic Properties of the Transactinides Electronic configurations. For other methods see [17].25] have shown again a different elec­ tronic configuration.16 eV higher in energy in good agreement with the “corrected” value of 0. indeed. shown that the strong relativistic stabilization of the 7p orbitals ground state in contrast to the ground state results in the shown by single-configuration DF calculations [23].5 eV [24] or 0. From knowledge of trends in these properties one can assess the similarity of the heaviest elements to their lighter homologues in the chemical groups. The configuration proposed in [87] as the ground state turned out to be 2. 5. was found to be about 0. polarizabilities and stability of oxidation states are important atomic properties. For elements 105 through 108. [24] taking into account correlation effects by the configuration mixing have.24 eV [25] higher in energy. The ground state of Rf was.. More accurate CCSD calculations [86] confirmed later this result. Inclusion of correlation effects of higher orders (f-electrons) in the CCSD calculations resulted in the inversion of the and configurations with the latter being more stable.g. Differences in the chemical behavior of the transactinides and their lighter homologues can result from larger ionic radii.186 eV of the MCDF calculations [24]. like. The CCSD calculations also confirmed the electronic configurations of elements 111 and 112 [89. ionization potentials (IP). as well as the .46 The Chemistry of Superheavy Elements limitations. the MCDF calculations [24. the MCDF calculations confirmed the ground states [27-29]. e. however.

Os or Hg. IPs.2 ORBITAL ENERGIES. as was predicted by the DF [12] and the DFT [95] calculations. the relativistic stabilization of the and electrons was a reason to suggest an enhanced stability of lower oxidation states like or and to design gas-phase experiments to detect a p-character of Lr and Rf taking into account different volatilities of d. are shown in Figure 9. the through 118 [30] have also given the relativistic stabilization of the 7s electrons of the transactinide elements results in the stability of the electron pair in the ground and first ionized states over the entire row of the Periodic Table. The MCDF calculations of multiple IPs for elements 104 through 108 [26-29] and estimates of redox potentials (see Section 7. 5.and p-element compounds.3 eV higher in energy in contrast to the state of Hf. For element 121. accurate CCSD calculations were reported for elements heavier than 118 [94.4 eV. The lowest state of element 121 anion is compared to the state of [35]. W.2. For some time. see Table 2.. 114 and 115 [91-93] obtained by the earlier DF and DS calculations. Thus. the CCSD calculations have given the configuration [35]. the CCSD calculations [33] have given the ground state in contrast to the state for Th. This configuration is a result of the relativistic stabilization of the electrons and is lower than (which is the ground state for the lighter group-3 homologues) by 0. experimental in the case of the 5d elements and calculated for the 6d elements (at the CCSD and MCDF levels).16]. The MCDF calculations for elements 113 state as the ground. The relativistic stabilization of the 7p electrons manifests itself in some excited states different than those of the lighter homologues. of Rf lying 0. Neither was the character of Rf confirmed by molecular calculations. (The non­ [89]). relativistic configuration of element 111 is.33].35.g. e. IONIZATION POTENTIALS AND OXIDATION STATES The non-relativistic (HF) and relativistic (DF) orbital energies [23] for elements 104 through 118 are shown in Figure 8. for example. For element 122. see [15. Single IP are listed in Tables 2 and 3. of Ta. which is and different from the states of some elements of the row like or from the 1+ ionized states. Recently.1) did not confirm the stability of lower oxidation states. the nearest homologue: the relativistic stabilization of the 8p orbitals is responsible for such a change. Theoretical Chemistry of the Heaviest Elements 47 ground states for elements 113. .

48 The Chemistry of Superheavy Elements .

are very similar. respectively.33]. The IP of Sg and Bh are very similar to those of W and Re. The calculations [26-29] have shown the multiple IP to decrease within the transition element groups (Figure 10). The reason for that is the proximity of the relativistic valence 7s and 6d orbitals (Figures 6 and 8). and some CCSD values for elements 112-115. Due to the same reason lower oxidation states at the beginning of the 6d series will be unstable: the step-wise ionization . That makes the excitation energies of the 6d elements smaller than those of the lighter 4d and 5d homologues. the ionization energies from those orbitals are also similar. They are useful in estimates of stabilities of higher oxidation states.2. Theoretical Chemistry of the Heaviest Elements 49 The shape of the lines in Figure 9 reflects the energy level structures shown in Figure 8 and the ionization processes. Multiple MCDF IPs for elements 104 through 108 are given in [26-29]. This is due to the fact that the ionized states are different in and and and respectively. resulting in an enhanced stability of the maximum oxidation states. 121 and 122 are given in [9093.35. in contrast to and or and Since the energies of the 6s orbitals in W and Re and of the 6d orbitals in Sg and Bh.

Due to a relatively high electron affinity of element 111. be active in element 112.g. Since the 6d orbitals of the 6d elements are more destabilized than the (n-1)d orbitals of the 4d and 5d elements.43 eV.oxidation state can then be stable with appropriate ligands. an increase in the stability of the highest oxidation states can be expected.97 eV is the largest among those of all the con­ sidered elements [90]. Thus. . the 6d electrons of element 112 should play an important role. The 1+ oxidation state was predicted to be very unstable [12]. The first ionized electron of element 112 is a 6d excited state in contrast to the state of electron resulting in the Hg.50 The Chemistry of Superheavy Elements process shown in Figure 11 for group-6 elements. however. The IP of element 112 of 11. 1. e. The 6d orbitals should. of the 3+ and 5+ states of element 111. though less sidered to be the most inert out of all the elements of the inert than Xe. Together with its closed shell configuration this is the reason why element 112 is con­ row. the IP of Hg is 10. results in the and not in the configurations for or [99]. the and will even be less stable than and The destabilization of the 6d orbitals at the end of the transactinide series is also the reason for the 6d electrons to be chemically active. As a conse­ quence. for comparison. or d-d metal interactions should be more active in element 112 compounds than in those of Hg. 4+. The EA of element 112 is 0. That may mean that higher oxidation states. as an example.

hence. results in the closed-shell configuration of element and a little participation of the electrons in bonding. see Figure 8. therefore. However. is the reason for an enhanced stability of lower oxidation states at the beginning of the 7p-series. The DCB CCSD result of 8. That suggests that the 2+ state should predominate over the 4+ state to a greater extent than in the case of Pb. Theoretical Chemistry of the Heaviest Elements 51 The large relativistic stabilization of the electrons and. The increased stability of the orbital is also the reason for the highest EA(113) = 0. the 1+ oxidation state will be more important for element 113 than the 3+ state. a large 7s­ 7p gap hindering the hybridization. The 5+ state was. though the first IP is still very high: IP(113) = 7. thus implying its relative inertness.2.1 eV for element tic reduction in the as compared to 8 eV for Thus. The 6d orbitals should be still acces­ sible for hybridization at the beginning of the 7p series (elements 113 and 114) and should take part in bonding leading to the formation of higher oxi­ dation states. suggested as stable in The very large SO splitting of the 7p electrons. the relativistic stabilization of the 7s orbital results in a drama­ excitation energy to 0.306 V is the largest in group 13 as compared to IP(Tl) = 6.539 eV is the most accurate [92].108 eV. The first IP of element 114 was calculated by quite a number of methods. the 2+ or 3+ oxidation states were thought to be probable for element 113. see Figure 8.68 eV [91] in the group as compared to EA(Tl) = 0. The trend to an increase in the IP in the group is continued with element 114 due to the relativistic stabilization of the .4 eV. Due to the inertness of the electrons. see Table 3.

For element 118. see Table 3. element 118 is expected to be the least .36 eV. the calculations [98] show its IP to be about that of element 114 and less than IP(Rn) = 10. element 116 should be stable in the 2+ oxidation shell. which is three times larger than due to a very large the splitting of the 6p elements. The EA is predicted to be zero [96] within a given accuracy of the DFC CCSD method due to limited basis sets. as compared to EA(Pb) = 0.52 The Chemistry of Superheavy Elements electrons. Element 117 has one electron missing at the relativistic stabilization of the shell it should. therefore.97 eV.74 eV and IP(112) =11. The 1. the IP of Sn and Pb are 7. respectively. be more stable in the 1+ and 3+ oxidation states than the lighter homologues. In element 115. therefore. Due to the smallest IP in group 18.oxidation state becomes less important in group 17 due to the destabilization of the orbital (the EA of element 117 is the smallest in the group [12]). be important. element 114 should form coordination compounds like the hexafluoride The plot in Figure 9 shows a sharp decrease in IP from element 114 to 115 SO splitting. Due to the state.42 eV. Because of the relatively destabilized 6d shell.34 eV and 7. 1+ oxidation state should. For comparison. since an electron is added to the destabilized orbital. Consequently. but less stable in the 5+ and 7+ oxidation states.

The CCSD IP of element 122 is 5.2. due to the participation of the expanded The IR of elements 104 through 108 in various oxidation states were estimated on the basis of a linear correlation between obtained from the atomic MCDF calculations [26-29] and experimentally known IR for their .31 eV to 4. The latter case is expected for compounds of the transactinides in higher oxidation states where the 6d orbitals are involved.59 eV as compared to the IP of 6. The situation is more complex when both types of the orbitals participate to an equal extent in bonding (see further discussion for 111H). while the (n-1) orbitals expand. ATOMIC/IONIC RADII AND POLARIZABILITY An ionic radius of an element is defined by the maximum of the radial charge density. as the DK CCSD calculations show [102]. being the highest in group 1. except for element 113 (where contracted mostly to bonding). see Figure 6. As discussed earlier. For the 7p orbital contributes elements. the highest in group 3 [35]. The DF and DPS IPs of heavier elements can be found in [12]. It was predicted to form compounds with F and even Cl.52 eV for Th [33]: this relative decrease is due to the ionized electron of element 121.45 eV and EA(121) = 0. while those with the predominant contribution of the (n-l)d orbitals should increase. The outer 8s orbital of element 118 is relativistically stabilized to give the atom a positive EA = 0. the relativistic ns orbitals contract within the chemical groups. The smallest of the 7s orbitals of element 112 suggests that the 112-X bond length should also be the smallest.3 RADIAL CHARGE DISTRIBUTIONS. Due to the relativistic stabilization of the 8s orbital. Similar calculations did not give a bound state for The IP of element 119 is relativistically increased from 3. The inclusion of both relativistic and correlation effects was required to obtain this result. The oxidation states 2+ and 4+ will be more important than the 6+ state because of the relativistically stabilized electrons. The calculated CCSD IP(121) = 4. of an outer valence orbital.056 eV according to the DCB CCSD calculations [101]. 5. EA(119) = 662 meV. bond lengths are expected to increase within the groups orbitals. Theoretical Chemistry of the Heaviest Elements 53 inert and the most electropositive out of all noble gases. The MCDF for elements 104 through 108 are given in [26-29].53 eV. or by its expectation value The DF values for elements up to Z = 120 are tabulated by Desclaux [23]. This means that bond lengths in molecules with the predominant contribution of the 7s orbitals should relativistically decrease. according to the DCB CCSD calculations [94].57 eV.

u. while the IR of the transactinides are about 0.u.102]). They are summarized in Table 4 and Figure 10 for these elements in the highest oxidation states..54 The Chemistry of Superheavy Elements lighter homologues [103].u. as was calculated at the CCSD(T) level [102]. 6. Therefore. As a consequence. Relativistically decreased atomic sizes and increased IPs of the 6d elements are related to relativistically decreased dipole polarizabilities. The IR of the lighter 6d elements are however smaller than the IR of the actinides since the latter undergo the actinide contraction of 0.u.05 Å larger than the IR of the 5d elements due to an orbital expansion of the orbitals being the outer orbitals for the maximum oxidation state. These were the first gas-phase compounds studied experimentally.82 a.83 a.108].. For element 119. as was shown by the PP CCSD(T) calculations [107. there was widespread interest in their electronic structures and fundamental properties .94 a. decreased from 693. Relativistic effects on change roughly as For element 112. The data of Table 4 and Figure 10 show that the IR of the 4d and 5d elements are almost equal due to the lanthanide contraction which is 86% a non-relativistic effect. should be the smallest in the group and in the row. The polarizability of 118 is expected to be the highest in the group suggesting its highest reactivity.030 Å which is mostly a relativistic effect [13. and it is relativistically decreased from 74. to 25. to 184.66 a. The Electronic Structure and Properties of Gas-Phase Compounds. element 112 should form the weakest van der Waals bond and is also relativistically should be extremely volatile. Role of Relativistic Effects Transactinides are now known to form volatile halides and oxyhalides as do their lighter homologues in respective chemical groups. (The latter were shown to change linearly with [106.105].

Re and Bh) [113]. Results until 1999 are overviewed in [15. such as (M = W and Sg). Mo. The influence of relativistic effects on the electronic structure and properties of the 6d transactinides was analyzed in detail on the example of (M = V. Theoretical Chemistry of the Heaviest Elements 55 such as ionicity or covalence. and (M = Mo.03 Å larger than than The relativistic contraction of orbitals and the relativistic contraction of bond lengths were shown to be two parallel. Various electronic structure properties such as IP. (M = Ru. W and Sg).16. (M = Ti. Thus. geometries were performed for (M = Tc. Results of the ab initio DF calculations were reported for [116]. charge density distribution and bonding. Ta and Db). Ta and Db) [117]. The calculations showed a decrease in the dissociation energy of as compared to that of and a slight increase in it of as compared to that of 6. Os and Hs) [114] using the RGGA DFT method. as well as their trends have been predicted for the transactinides and their lighter homologues. Hf and Rf) and (M = Cr. Nb. mostly the DS-DV. Nb. and ( M = Ta and Db) [115]. 6. W and Sg) are the simplest systems which were used quite a time ago as models to study the influence of relativistic effects on molecular properties. Zr.110]. but largely independent effects. The calculations of binding energies and optimization of (M = Ti. electron transition energies. EA. 105 and 106 Using density-functional methods. and and (M = V. and (M = Mo. Opposite trends in the relativistic and non­ relativistic energies of the valence orbitals from the 5d to the 6d elements were shown to result in opposite trends in molecular orbital (MO) energies. W and Sg) [112].1. see Figure 12. a large series of calculations was performed for halides and oxyhalides of elements 104 through 106: (M = Zr.2 Halides and oxyhalides of elements 104. Hf.06 Å larger is only 0. CCSD RECP calculations were also performed for halides and oxyhalides of elements 104 through 106.1 Hydrides of elements 104 and 106 The group-4 and 6 hydrides.1. and Rf). Zr.1 ELEMENTS 104 THROUGH 108 6. The question of the magnitude of the influence of relativistic effects on those properties was also of great interest. The DP one-center expansion (DF-OCE) calculations [109] showed relativistic effects to decrease the bond length of and so that and is 0. bonding and thermochemical stability. as well as trends within the groups. the highest occupied MO (HOMO) of the 3p(Cl) . Recently.2. Hf and Rf) [111].

the trend would be opposite from unoccupied MO (LUMO) of predominantly (n-1)d character. A relativistic increase in the energy gap between the HOMO and LUMO and.56 The Chemistry of Superheavy Elements character. Ta and Db) in Figure 13. the EA decrease in the group as a result of relativity. non-relativistically. would have been even less stable than The Mulliken analysis [122] of the valence orbital populations has shown the bonding in the 6d-elements to be dominated by a large contribution of both . is. responsible for the DP. in turn. destabilized in each compound and becomes more destabilized from the Ta to Db molecule due to the relativistic destabilization of the (n-1)d orbitals. Non­ to The lowest relativistically. responsible for EA. in the energy of the lowest charge-transfer transitions associated with the reduction of the metal is indicative of the increasing stability of the maximum oxidation state. This is shown by a correlation between and reduction potentials for (M = V. Thus. Consequently. Nb. compound and becomes more bound from molecular IP increase in the group due to relativistic effects. is relativistically stabilized in each to Consequently. hence.

Some earlier estimates of obtained via a correlation between OP and covalent part of the binding energy (deduced from the experimental dissociation enthalpies minus the calculated Coulomb contribution into it) are also given there [123]. see Figure 14. e. The 7s. bonding and stabilities of oxidation states in going over to the 6d elements. therefore. EA. Effective charges were shown to decrease in the group and overlap populations (OP) to increase.. relativistic effects define continuation of the trends in the IP. as well as both the contribute about 15 % to the bonding. see Figure 15. the trends would be just opposite from Ta to Db due to the opposite radial distributions of the atomic wavefunctions and their energies. (M = W and Sg) using both the DFT [111-114] and RECP [115] methods are summarized in Tables 5 and 6.g. while the non-relativistic description of these properties would give opposite and. The calculated and for (M = Ta and Db). Thus. Theoretical Chemistry of the Heaviest Elements 57 the and orbitals. wrong trends. A comparison of the relativistic with non-relativistic calculations shows this increase to be a purely relativistic effect due to the increasing contribution of the relativistically as well as of the expanded 6d AO stabilized and contracted 7s and in bonding. . 70% in typical of d-element and orbitals. (The OP is an amount of the electronic density located on the bond between atoms in a molecule and is a direct counterpart of the covalent contribution to the binding energy [122]).2. each compounds [117]. Non-relativistically.

58 The Chemistry of Superheavy Elements .

were shown to be unstable with respect to the loss of Cl and to transform into compounds of [112]. thus indicating that the former procedure is justified. Both types of the data also agree with an increase in the stability of compounds with increasing number of oxygen atoms from to and to (M = Mo. It is also notable that earlier estimates of made by using ionic and covalent contributions to the binding energy deviate very little from the RECP values. Theoretical Chemistry of the Heaviest Elements 59 The data of Table 6 show good agreement for of between the RECP [123] and DFT calculations.2. as is experimentally known for the lighter elements. . Thus. indeed. experimentally observed [124. W and Sg).125]. was recommended [123] for the high-temperature gas phase experiments as the most stable 106 compound and and was. What is more important. a trend to a decrease in the values from the W to Sg compounds found in [123] was confirmed by the RECP calculations [115].

for group-6 oxyhalides are given in Table 7. The obtained MO energies for are very similar to those of indicating close analogy in properties between the com­ and pounds. with the values being very similar. 6. so that the trioxyhalides and Re. the most stable and most volatile species among oxychlorides of these ele­ ments. ground state electronic Relativistic effects were shown to stabilize the configuration in DbO.60 The Chemistry of Superheavy Elements The authors of [115] evaluated contributions of spin-orbit and correlation effects into bonding for these compounds. The optimized geometrical structures are given in Table 8 showing a of 0. The effects are larger for the Sg compounds than for the Rf due to an splitting. but both values show an increase in from the W to Sg oxyhalide. The Mulliken population analysis data and OP). Both the DFT and RECP results show a decrease in and an increase in OP from the W to Sg compounds. and its homologues Tc media. Re and Bh The first chemical experiment for element 107. The RECP are somewhere larger than the DS-DV ones. the electronic structures of (M = Tc. the of becomes increasing 1. in contrast to the state of NbO [57]. To predict the outcome of the experiment.2 eV smaller than the of Electron correlation effects on were found to be larger in the W compounds than in the Sg compounds and they become more significant as the number of oxygen atoms increases.1.05 Å from the experimental values small deviation of the calculated for In Table 9. Re. The PP calculations were performed for DbO along with NbO and TaO. As a consequence.3 Oxyhalides of group-7 elements Tc. as that in TaO. was conducted in the and are known to be (M = Tc. Bh. as well as dipole moments. and Bh) were formed [9].5 eV for the transactinides molecules at the CCSD(T) decrease in level. The SO interaction causes a of 1-1. and are presented as a result of . Re and Bh) were calculated using the RGGA DFT method [113].

and were performed using the DFT method [114]. The dipole moments increase from the Tc to the Bh compound similarly to the group-6 oxyhalides. The polarizabilities also increase in this direction. The data of Table 9 were used to predict adsorption enthalpies of on the surface of the chromatography column for the gas-phase chromatography experiments [9] (see Section 6.54 eV. the electronic structure calculations for the group-8 gas-phase tetroxides. Hs. thus. The RGGA for agrees well with the thermoche­ mical with the difference of 0. 6.1. The Mulliken analysis data of Table 9 show to be more covalent (a and Such an increase in covalence is typical larger OP) than of halides and oxyhalides of the elements at the beginning of the trans­ actinide series (Rf.2.1. To predict the outcome of the first gas-phase experiment on Hs [10]. to form a very volatile tetroxide. and Os.4 Tetroxides of group-8 elements Ru. The RLDA values are closer to the experimental values than the RGGA ones. Theoretical Chemistry of the Heaviest Elements 61 the calculations. Db and Sg) and this is a relativistic effect as discussed earlier. The “experimental” for was predicted by correcting the calculated value by the difference between the calculated and experimental values for the lighter homologues. was expected to be a member of group 8 of the Periodic by analogy with Ru Table and. Os and Hs Element 108. Optimized are shown in Table 10. .6).

This is a relativistic effect caused by the relativistic destabilization of the 6d and are given in Table 10 in very orbitals. and equal to the IP of slightly lower according to the total energy calculations. The calculated good agreement with the experiment for the IP. and this increase is a result of the relativistic orbitals and stabilization and contraction of the valence 7s and destabilization and expansion of the 6d orbitals. is more and Such an increase in covalence has the same covalent than relativistic origin as that for all other group-4 through 7 compounds.6). An increasing value of the energy gap between HOMO and LUMO is indicative of an increase in the stability of the 8+ oxidation state from Ru to Os. In these transactinide compounds. 6.1. The covalence increases within the groups. see Figure 16. halides and oxyhalides of group-4 through 8 elements.5 Comparison of properties of group-4 through 8 halides and oxyhalides The DFT and RECP calculations predicted similar trends in the electronic structure and related properties for oxides. bonding is defined by and orbitals. as values indicate that should be more stable discussed earlier. The The calculated molecular properties (Table 10) were used to than predict adsorption enthalpies of the group-8 tetroxides on the surface of the chromatography column for the gas-phase chromatography experiments [10] (see Section 6. The calculated show a “saw-tooth” behavior in the group. . As expected. The IP of is almost according to the transition-state calculations.62 The Chemistry of Superheavy Elements The calculated MO energies of are very similar to those of and indicating their close analogy.1. with a large a strong participation of both the admixture of the 7s and orbitals. and further to Hs in the tetroxides.

and from the 5d to the 6d compounds within the same group. The Figure 17. reflect the experimentally known similarity of the bond lengths . The other reason is a decrease in the ionic contribution to bonding which is also a relativistic effect. one should mention a decrease in the metalligand bond strength of the halides with increasing group number. connected with a decrease in the relative stability of the maximum oxidation values. found a similar decrease in relativistic effects steadily enhance bonding with increasing Z. was shown should not exist. This is one of the reasons for most of the transactinide compounds having atomization energies lower than those of the 5d homologues.5 eV at the 6d compounds [115]. Consequently. see Figure 13 in [15]. This is also to be unstable [15]. see state along the transactinide series. In all the groups.2. Thus. To put the various calculated data on the same footing.1. Among other important trends. Theoretical Chemistry of the Heaviest Elements 63 Trends in and for various types of compounds are summarized in Figure 17. The data of for the lighter compounds) Figure 17 show a decrease in from 5d to the 6d elements for almost all and though the DFT calculations have the compounds except for from to [112]. the experimental for the 4d and 5d compounds and “extrapolated” (corrected by the difference between the calculated and experimental values for the transactinides were used. though increasing SO splitting of the d orbitals partially diminishes it reaching about 1 .

One should note here that and are relativistically decreased due to the relativistic increase in IP. The values are then correlated with the The latter is then related to the sublimation adsorption enthalpies enthalpy a property of the macro-amount using some models. decrease in the molecular size and increase in the covalence of the compounds. Available experimental data are often contradictory and hardly correlate with a single electronic structure parameter.1. An increase in of the low symmetry molecules and an increase in within the groups are observed for all the considered compounds.64 The Chemistry of Superheavy Elements for the 4d and 5d compounds (the lanthanide contraction effect) and an increase in about 0.6 Predictions of volatility for group-4 through 8 compounds Identification of properties of the transactinides by studying their volatility is a difficult task due to the fact that there are several quantities associated with this phenomenon.05 Å in the 6d compounds in comparison with of the 5d compounds. see . 6. the measure of volatility is assumed to be either a deposition temperature in a thermochromatography column or the temperature in an (isothermal) column at which 50% of the desired product (50% “chemical yield”) are passing through the gas chromatography column [8]. In the gas-phase chromatography experiments.

higher OP of the group-5 halides compared to those of the group-4 halides are consistent with their higher volatility.. e. increasing dipole moment s of the low symmetry compounds of the group-5 group-6 or group-7 are the reason for the observed decrease in volatility within those groups. To find a way out.16] yielded data that permitted establishment of some relationships between molecular properties such as covalence or dipole moment and volatility. As a result of these theoretical considerations it was predicted that volatility should change as [16. see Section 6.7. This was. The largest of lower symmetry transactinide compounds should result in their lowest volatility as compared to those of the lighter homologues within the groups.2.131. the quartz can be covered with a reactive material. points basically correlate with A larger series of the DS-DV calculations [15. measurements of the adsorption temperatures or Some hypothetical was predicted for transactinide compounds [130]. see the Chapter 7. Theoretical Chemistry of the Heaviest Elements 65 Chapter 6. is presently a formidable task for quantum chemical calculations. the following relationships have been established for the group-4 through 8 highest halides and oxyhalides: higher OP of the 5d halides compared to those of the 4d halides correspond to their higher volatility.113]. These observations led to conclusions that the higher covalence (larger OP) of high symmetry halides or oxides of the transactinides should result in their higher volatility compared to their 4d and 5d homologues.g. smaller OP of oxyhalides compared to those of the corresponding pure halides are related to their lower volatility. To determine of a very heavy molecule on a surface often of a vaguely known structure.9]. Thus. the equilibrium vapor pressure over a substance. some models accounting for physical adsorption with the use of the . Boiling however.1. indeed. Experimentalists were also advised to use the equilibrium vapor pressure of the lighter homologues as a benchmark for the “one-atom-at-a-time” of the chemical yield.123.125. much lower OP of halides of the actinides compared to those of halides of the d elements are in line with the lower volatility of the actinides.124. confirmed experimentally by the observation of higher volatility of than that of [132] and lower volatility of in comparison with those of their lighter homologues or [133. The most accepted measure of volatility in macro-chemistry is.

Thus. The calculated contributions to E(x) for a typical value of Q(Cl) = -0. Experimental volatility studies of (M = Ru. dipole-polarizability and the van der Waals (dispersion) interactions [134]. so that the interaction of should take place via an outer Cl atom carrying some effective charge. The data there are indicative of an increase in the energies of all three types of interactions from the Tc to the Bh compound.114].66 The Chemistry of Superheavy Elements calculated molecular electronic structure properties were applied to predictions of [113. the interaction should be of a pure van der Waals type.4 are given in Table 11. The obtained adsorption enthalpies show that volatility changes as The are in excellent agreement with predicted sequence and the experimental values of –51 ±2 kJ/mol and –77 ± 8 kJ/mol for and respectively [9]. In the experiments on studying volatility of group-7 elements [9] a mixture of and HCl was used to produce the volatile (M = Tc. the quartz chromatography column was supposed to be covered with adsorbed HCl. For these highly symmetric molecules having no dipole moments. With the use of a model of the molecule-slab interaction and the relation between the dielectric constant of . The models are based on the principle of intermolecular interactions subdivided into usual types for the long-range forces: the dipole-dipole. Os and Hs) were performed in a chromatography column with a pure quartz surface [10]. Re and Bh). so that the interaction energy where (roughly IP) and belong to the molecule and those with index “slab” to the surface. The long-range forces equations were modifies accordingly [113]. The interaction distance x for was deduced by setting the calculated E(x) to the experimental Assuming then the proportionality between x and molecular size and were determined using the calculated E(x) of Table 9.

Theoretical Chemistry of the Heaviest Elements 67 a molecular solid and its polarizability. The calculated contributions to E(x) between (M = Ru. found that indicating that the Hs oxide is less volatile [10]. Thus. and when the oxygen has an effective charge. and is the dielectric constant of quartz. In experiments with Os and Hs. the volatility of group-8 tetroxides in the particular experiments was expected to change as This sequence would be in accord with an idea of increasing volatility with increasing covalence of the compounds. condenses at a higher temperature than however. Because so few events were detected it is premature to say whether or not the experimental data are in disagreement with the predictions.2. It would be very interesting to discuss the of these molecules. Equal volatilities of and are also expected from the extrapolation within the group [135]. i. This can be influence of relativistic effects on the done after non-relativistic quantum-chemical calculations are performed. the interaction energy is expressed in the following way [114] where denotes roughly IP of the molecule and the slab.7 Summary of the volatility studies Observed trends in volatility of group-4 through 8 compounds compared to the theoretical predictions are summarized in Table 13.e. Os. performed under similar conditions. Similar expressions were obtained for the cases where the surface is covered with molecular oxygen. by setting the interaction energies from Table 12 equal to the experimentally known and were obtained. Using the same technique to define x as previously used in the case of the group-7 oxychlorides. . it was. and Hs) and the various types of surfaces are shown in Table 12. 6.1.

The calculations have shown to be very similar to with very close values of IP. The properties of 111H predicted by various calculations (HE.1 Dimers and fluorides of element 111 The relativistic contraction of the 7s orbitals (“Group 11 maximum”) results in the atomic size of element 111 being similar to that of gold and smaller than that of silver. see Section 3. For compounds. PP. 6. though the SO splitting diminishes it by 0.68 The Chemistry of Superheavy Elements 6. a sort of a test system like AuH. DK.) are compared in Table 14. A comparison of the relativistic (DF or ARPP) with the non-relativistic (HF or NRPP) calculations shows that the bonding is considerably increased by relativistic effects doubling the dissociation energy. The data demonstrate importance of relativistic and correlation effects. was studied in detail. PP CCSD(T). A more extended table can be found in [17.50]. etc. Relativistic effects were shown to be as large as crystal-field splitting.3. This is in agreement with the BDF . where the 7s orbitals contribute predominantly to bonding. The electronic structure of the simplest molecule 111H. the smallest size of the element 111 species in the group is expected. see the figure in [50]. The large relativistic destabilization and expansion of the 6d orbitals are also expected to influence their chemistry. DF. 6.2 ELEMENTS 109 AND 110 Molecular calculations [136] were performed only for using the DS­ DV method.3 ELEMENTS 111 AND 112 The special interest in the chemistry of elements 111 and 112 originates from the expectation of anomalous properties of their compounds as compared to homologues in groups 11 and 12 due to the predicted maximum of relativistic effects on the 7s electron shell. from AgH to AuH turned out to be inversed the trend to an increase in from AuH to 111H.7 eV (the ARPP CCSD – SOPP CCSD difference). Thus. DFT.

however. A. stable in the group. The PP CCSD calculations have shown that is substantially shortened by relativity. so that the question about the right trends remains open.72]. Theoretical Chemistry of the Heaviest Elements 69 calculations [72]. AuH and 111H. however. lower Relativistic effects follow a similar pattern as that in 111H except for 111F and 111O where the SO splitting increases The PP [107] and BDF [72] calculations show. to be Both types of the calculations show the trend to an increase in continued with 111H having the largest value of all known diatomic molecules. Br. the 111 compounds have slightly longer bond lengths (relativistically increased due to the radial extension of the but higher in comparison with those of AuX [72]. .137]. orbitals). 111) show that except for the oxide. Cl.2. and it is the smallest in the series AgH. Au. The BDF calculations. In [72]. energies of the following de­ composition reactions and were calcu­ lated on the PP MP2 and CCSD levels [107. The was shown to be relativistically decreased from AgH to AuH and to 111H indicating that 111H is more covalent and element 111(I) is more electronegative than Au(I) [50. The SO coupling stabilizes the molecules in the followThis order is consistent with the relative ing order: involvement of the (n-1)d electrons in bonding for each type of molecules. so that the trend to a decrease in is continued with 111H [50]. The DFT calculations for other dimers AuX and 111X (X = F. much larger SO effects were found on (SO increased) and (SO decreased). O. To study the stability of higher oxidation states. show to be slightly longer than The different trends in obtained in these two types of the calculations are obviously connected with a different contribution of the contracted 7s and expanded 6d orbitals to bonding (though the 6d contribution was found to de predominant in both cases). different trends in and from AuF to 111F. The results confirmed the fact that relativistic effects stabilize higher oxidation states due to a larger was shown to be the most involvement of the 6d orbitals in bonding.

3. so that the difference in between HgX and 112X might be rela­ of Hg and element 112 on the metal surfaces. The Mulliken population analysis shows this decrease to be a result of the drastic relativistic stabilization and. inertness of the shell leading to a large decrease in the 7s(112)-6s(Au) overlap compared to the 6s(Hg)-6s(Au) one. Since the most exciting property of element 112 is its predicted high volatility [12. The calculated are shown in Figure 18 together with experimental of Hg on the corresponding metal surfaces [143]. The calculations revealed an increase in of about 0. To predict the outcome of those experiments on the quantum-mechanical level. Element 112 and its nearest homologue Hg are supposed to be sorbed on Au and Pd metal detectors [11]. the DFT calculations describe the bonding in these systems correctly. Pd. Element 112 is expected to have adsorption enthalpies on the Au and Pd surfaces between those of Hg and Rn. the ability of element 112 to form intermetallic compounds was tested by the DFT calculations for 112M. is indeed. element 112 is expected to be more weakly adsorbed than Hg. Pt. Thus. ted to the difference in Thus. The contribution of the other valence orbitals is almost unchanged. The PP calculations [108] have.2 Dimers and fluorides of element 112 The relativistic effects maximum on the 7s electronic shell in element 112 was confirmed by molecular calculations.06 Å and a decrease in of about 15 – 20 kJ/mol from HgX to 112X. As a first step. as semi-empirical estimates of show [138. where M = Cu. The plots in Figure 18 show good agreement for the trends between the two types of data. with the interaction of Hg and element 112 with Pd being the strongest.138-140]. therefore.141]. Ag and Au [142]. calculations of adsorption of Hg and element 112 on metal surfaces of interest are highly desirable. The Mulliken population analysis for and (M = Hg and 112) [108] suggests that the 6d orbitals of element 112 should be involved in bonding to a larger extent than the 5d orbitals of Hg. experiments are planned to detect this element in its elemental state by gas-phase chromatography separations. the experimental for Hg and the calculated for HgM and 112M. shown that the relativistic bond length contraction in similar to that in 111H. though . and that is the shortest among and and is similar to Due to relativistic effects should be the most stable in the group-12 hydrides. The calculated energies of the decomposition reactions and have confirmed the conclusion that the 4+ oxidation state of element 112 will be accessible and the 2+ state not [12].70 The Chemistry of Superheavy Elements 6. The neutral state of element 112 should also be more preferred than that of Hg.

6. The RECP CCSD calculations [100. A large spin-orbit contraction of the orbital results in the large SO contraction of the 113-H bond: Å according to the RECP Å according to the DFC CCSD(T) calculations [146] and CCSD(T) and PP SO CCSD(T) calculations [100]. Calculations of adsorp­ tion of Hg and element 112 on the metal surfaces are in progress using the embedded cluster model [144] For the case of adsorption of element 112 on the quartz surface. simple calculation [145] of the van der Waals interaction of Hg and 112 using the slab model (see Section 6.2. In 113H. The results are summarized in Table 15. Theoretical Chemistry of the Heaviest Elements 71 not as weakly sorbed as was expected earlier [138]. The .4 ELEMENTS 113-117 The very large SO splitting of the 7p orbitals is expected to influence properties of compounds of elements 113 through 117.90] have given as compared to 34 kJ/mol and Thus. This also agrees with the of 113H is the only case of the bond RECP CI calculations [148]. the adsorption properties of element 112 are expected to be between those of Hg and Rn.1) and the calculated and IP of element 112 [108. the 6d and 7s orbitals were shown to participate little in bonding and all the effects are defined by the large participation of the shell.146-147] were performed for simple MH (M = 113-118) to study the influence of relativistic effects.

will probably be unstable since the energy of the reaction is less than -100 kJ/mol [100].107. Participation of the 6d electrons of element 113 in bonding was confirmed by the PP calculations [100] for and and RECP for [147]. as the DF calculations show [149]: the bonding and antibonding character. The stability of the high-coordination compound with the metal in the 5+ oxidation state is foreseen. so that [146] and PP [100] in good RECP agreement with each other. Thus. bond having The PP and DCB calculations [100. the SO interaction should change the sign of the dipole moment. Tl and even Al. should also be weakly electron yields a weak bound. element 113 was found to be more electronegative than Ga.147] for MF (M stands for all group 13 metals) have shown increasing and from TlF to 113F.146]. in contrast to and decreasing values from T1H to 113H [146]. The reason for that is the large atomic SO and from BH to 113H were destabilization of element 113. As a consequence of the involvement of the 6d and orbitals. These different trends in for the MF compounds as compared to MH are explained by a more ionic nature of the MF molecules. The calculated energies of the decomposition . In. a reversal of the trend to an increase in and was predicted from TlH to 113H [100. Decreasing predicted. a T-shape geometric configuration rather than trigonal planar was predicted for these molecules. The being of only academic interest.72 The Chemistry of Superheavy Elements contraction among all the MH (M = elements 113-118). For 114H through and expanded orbitals take part in 118H. The binding energy was shown to be destabilized by the SO effects. In the series of the group-13 hydrides. both the contracted bonding. with the former being gradually less available for bonding. For a dimer (113)(117). as the results of the DF calculations show [49].

Similar effects on the bond strengths like those on MH were found for these 114 compounds. Thus. Al. element 114 is expected to be less reactive than Pb. Thus. O. the reason why Å [146] is larger than Å. and as reactive as Hg. I. The inertness of element 114 is proven to be a combined result of both the SO splitting and the double occupancy of the spinor. see Table 15. In. The RECP of calculations for 114H have found a SO bond length expansion 0. Estimates of formation enthalpies of and for Po and element 116 [150] made on the basis of the MCDF atomic calculations confirmed the instability of the 4+ state of element 116.07 eV in RECP CI [100] and –2. much larger than that of PbH (­ 0. Theoretical Chemistry of the Heaviest Elements 73 reaction (M = B. . The neutral state was found to be more stable for element 114 than that for Pb. The possibility of the existence of is considered [96]. The SO bond strength decrease was found to be very large in 114H: -2.5 eV according to RECP CI calculations [100]) is the smallest in the series. The instability was shown to be a relativistic effect.030 Å [100]) in agreement with the BDF value of 0. Cl.2.068 Å [146] (0.71 eV) and the largest in the series of MH (M = 113 through 117). Relatively small for PbH and 114H in comparison with those for TiH and 113H were interpreted as the participation of both contracted and expanded orbitals in bonding. The electronic structures of 114X (X = F. The chemistry of element 116 is expected to be mainly cationic: an ease of formation of the divalent compounds should approach that of Be or Mn. A relative inertness of element 114 due to the closed-shell configuration was confirmed by calculations for some of its compounds.52].. shown by the RECP calculations (0. was predicted to be thermodynamically unstable in contrast to Energies of the decomposition reactions and (X = H. Tl and element 113) suggest a decrease in the stability of the 3+ oxidation state in the group. Br. The results show a decreasing trend in the stability of the 4+ oxidation state in the group in agreement with the predictions of [150] based on atomic calculations and simple models of bonding.02 in BDF calculations [73]. -2.18 eV in RECP [146].094 Å [73]. were calculated using the RECP. Ga.g. obviously. F and Cl) for group-14 elements were calculated at the PP CCSD(T) and DHF levels [96. and tetravalent compounds should be formed with the most electronegative atoms. This is also. e. ZORA and BDF methods [73].40 eV according to BDF [73] and 0.

therefore.146. Thus. The bonding in 117H. 6. a closed shell molecule.17 eV [155] in agreement with each other. A relatively high reactivity of element 118 was foreseen by earlier considerations [154. as in the case of Xe. however. An important observation was made that the fluorides of element 118 will most probably be ionic rather than covalent. The influence of the SO interaction on the geometry of was investigated by the RECP-SOCI [151] and RECP CCSD calculations [155].25 eV [151] and 0. In both papers it geometrical configuration for (calculated in was shown that a agreement with experiment) and for (calculated) becomes slightly unstable for A configuration was shown to be more stable than the in by 0. HAt and H117. the bonding in is predicted to have antibonding considerable character [17]. noble gases become less inert with increasing Z. the weakening and lengthening of the chemical bond is predicted by the DHF Å) [49] and RECP Å) [146] calculations. in element 117 should form dimers The DCB CCSD(T) calculations for (X = F through At) [152] found a considerable antibonding character of due to the SO coupling (without the SO coupling. Thus. The 117Cl is also predicted to be bound by a single bond and have the relativistically (SO) increased bond length [153]. The SO effects stabilize by a significant amount of about 2 eV. an increasing trend in and a decreasing trend are continued with H117. Rn and element 118 [155] confirmed an increase in the stabilities of the 2+ and 4+ oxidation states. increasing trends in and are continued with element 118. Element 118 was predicted to be the most electropositive in the group and to be able to form a 118-Cl bond. Thus. it is an the HOMO of orbital). since no non-linear at the HF level of theory.5 ELEMENT 118 In group 18. 2/3 of the bonding without the SO splitting. This prediction might be useful for future gas-phase chromatography experiments. The RECP calculations for the reactions and where M = Xe.12].05 Å.0 meV by the SO . Analogously to the lighter homologues. In the row HI. though they elongate by 0. The reason for that was the availability of only stereochemically active electrons for bonding. Thus.151]. claim that this modification should be applied with structure has been detected as a minimum caution. was shown to be formed by the orbital and is. Han et al [155]. RECP calculations [146] for 118H have shown the van der Waals bond to be stabilized by about 2.74 The Chemistry of Superheavy Elements The trend to a decrease in the orbital involvement in bonding in group 17 was found to be continued further with element 117 [49. a SO modification of the valence shell electron pair repulsion (VSERP) theory was suggested in [151].

Some general aspects of their chemistry can be found in [12. 7. 5 and 6 elements in acidic solutions [157.e. and and for the difluorides. So far. 118H « 114H < 112H for the hydrides.2. One of those correlations for group-6 species is shown in Figure 19.99] using results of the atomic MCDF calculations. . The redox potentials for the transactinides are summarized in Table 16. is very important for a chemical application. elements heavier than 118 were not studied at the MO level.99]. not always unanimous and varied depending on the model. The conclusions were.156]. Trends in the stability of various oxidation states of the very heavy elements were predicted earlier on the basis of atomic relativistic DF and DS calculations in combination with some models based on a Born-Haber cycle (see [12]). i. this topic received a more detailed consideration [157. Later. Thus. unknown values of redox potentials for the transactinides and some of their lighter homologues were determined for group-4.158.1 Aqueous Chemistry of the Transactinides REDOX POTENTIALS OF THE TRANSACTINIDES The knowledge of the relative stability of oxidation states. using the calculated MCDF IP [26-29] and experimentally known [159]. redox potentials. however. since where is a free energy of hydration being a smooth function of atomic number and it can easily be evaluated.. Theoretical Chemistry of the Heaviest Elements 75 effects and Å. could then be estimated using a correlation between and IP. For an oxidation-reduction reaction the redox potential is defined as where is the free energy of reaction (16) and F is the Faraday number. as an example. 7.Trends in molecular stability were predicted as follows: RnH « HgH < PbH.158.

The increasing stability of the maximum oxidation state is a relativistic effect.76 The Chemistry of Superheavy Elements Results of these estimates show the following trends in the groups and along the period: The stability of the maximum oxidation state increases in groups 4 through 6.2. will be unstable.157. Db and Sg in comparison with the lighter homologues can be found in [99. as is discussed in Section 5. respec­ tively. Along the row. Redox potentials for Rf.2. the stability of the maximum oxidation state decreases: or a similar trend for see Table 16. . see Figure 19 for Sg.158]. The reasons for that are dis­ cussed in Section 5. while that of lower oxidation states decreases. (The roman numbers denote the valence states in complex compounds). The estimates of redox potentials confirm that the 3+ and 4+ states for Db and Sg.

Consequently. . If one molecular complex.165].2. its distribution coefficient. in their extraction into an organic phase. i. This may change trends in the stabilities of complexes and. To define it in a straightforward way binding or total energies of species in the left and right parts of equation (20) should be calculated. competing with hydrolysis [163]. among many others is extracted into an organic phase. For a simple complex the cumulative complex formation constant is a measure of its stability. finally.2. dependent on is approximately a measure of its stability. Theoretical Chemistry of the Heaviest Elements 7.2 HYDROLYSIS AND COMPLEX FORMATION 77 Complex formation is studied experimentally by liquid-liquid extractions. Since it is almost impossible to do it with sufficient accuracy for very large.e. the following model was suggested by V. for elements of one group. a consecutive formation constant where is the free energy change of the reaction. One should distinguish between hydrolysis of cations and hydrolysis of com­ plexes. consecutive constants are used. or both. For step-wise processes. by calculating one can predict and understand sequences in the extraction of complexes into an organic phase or their sorption on cation or anion exchange resins. highly coordinated aqueous species. The former process is described as a process of a successive loss of protons In acidic solutions. a sequence in the values for a studied series. The complex formation is known to increase in the transition element groups. Thus. anion. and is competing with the complex formation described by the following equilibrium 7. hydrolysis involves either the cation. reflects a sequence in the stability of their complexes [162]. or anion exchange separations. however. Pershina [164.1 Theoretical model for the prediction of complex formation For a reaction like Equation 20. In aqueous solutions it is.

and are their where is a dielectric constant. the following expression for the free energy of formation of the species from the elements was adopted The first term on the right hand side of Equation 23. Kassiakoff and D. see Section 4. as it is shown in [167]. Thus. hydrolysis and complex formation constants were predicted for a large number of aqueous compounds of group-4 through 6 elements [164-170] in excellent agreement with experiment. is the difference in for the species in the left and right parts. 7.2.78 The Chemistry of Superheavy Elements In a fashion analogous to that of A. The accumulated experimental results have revealed quite a number of surprises and disagreements. Results of these calculations and comparison with experimental data reveal that a change in the electrostatic metal-ligand interaction energy contributes predominantly to all the trends in the complex formation can Thus. O. For a effective charges and reaction. and there were often disagreements in the sequences of the . see Section 2. just by calculating the correctly be predicted. The next term. For a reaction. coefficients and B should predict be then defined by fitting to experimental values for the lighter homologues. it was not clear whether Rf is more or less hydrolyzed than Hf. and overlap population.2 Element 104 Element 104 has extensively been studied experimentally. electrostatic contribution from M. Using this model. and the other is a conversion to the molar scale of concentration for the entropy. The last two terms are statistical: one is a correction for the indistinguishable configurations of the species.170]. OH. is the non- which is related to the where k is an empirical coefficient. To or for transactinide complexes. and for each compound are then calculated directly via Mulliken numbers implemented in the DS-DV or DFT methods. pairwise electrostatic (Coulomb) interaction: is a sum of each where is the distance between moieties i and j.2.3. P in Equation 23 is the partition function representing the contribution of structural isomers if there are any. OP. Harker [163.

show the following trend in hydrolysis for the group-4 elements (reaction 27): Zr > Hf > Rf. The predicted trend is also in agreement with the experimental data for Zr and Hf [163]. (26-29) are given in Table 17. The data. see [6] and Chapter 5. see the first line of Table 17. Theoretical Chemistry of the Heaviest Elements 79 values of group-4 elements obtained by their ion exchange separations from HF and HCl solutions. Hydrolysis of group-4 elements and their complex formation were studied theoretically [168] using the model described in the previous section. The following reactions were considered: the first hydrolysis step the step-wise fluorination process and the chlorination process The calculated for reactions of eqs. as compared to = 0.2. The first was then determined in good agreement hydrolysis constant with the experimental values of -2. since .3 and [163].6 ± 0. One should note here that a simple model of hydrolysis [163] implying that the hydrolysis changes with the ratio of a cation charge to its size would give the opposite and hence a wrong trend from Zr to Hf.7 [171].

i.3-0. since complexes with a higher charge are better sorbed on the CIX resin than those with a lower charge). however.3 Element 105 Hydrolysis of group-5 cations and Pa was studied theoretically [164] for the reaction . Taking into account the above mentioned arguments. indeed. this result cannot find its theoretical explanation. This was explained (and also shown by additional experiments) by a strong competition between and Rf complexes for adsorption on the active resin sites. Thus.80 The Chemistry of Superheavy Elements The following information can be deduced from the calculated For the cation exchange separations (CIX) performed at < 0. The weaker sorption of Rf from HF solutions of > M on the AIX column was.4 M HCl solutions [173].e. depending on whether the fluorination starts from hydrated or hydrolyzed species. the values will This is caused by the have the following trend in group-4: decreasing trend in the formation of the positively charged complexes (In the case of the formation of according to Equation 27: complexes with a lower positive charge from complexes with a higher positive charge (Equation 27) a sequence in the values is opposite to a sequence in the complex formation. the data of Table 17 suggest that the trend in the complex formation and values should definitely be continued with Rf: Zr > Hf > Rf. observed in the experiments on the CIX separations of group-4 elements at low HF concentrations [172]. For the AIX separations at 4-8 M HCl. For the formation of anionic complexes separated by the anion exchange (AIX) resins.. The TBP extraction of group-4 elements from 8 M HCl showed the of Rf in between those of Zr and Hf: Zr > Rf > Hf [175]. i. The AIX separations [174] of group-4 elements from aqueous 4-8 M values: Rf > HCl solutions have. This trend was. shown an inverse sequence in Zr > Hf.2. the trend becomes more complicated depending on pH. the trend for the formation of Such a trend was (Equation 28) is reversed within group 4: observed in the experiments on the AIX separations of group-4 elements from mixed 0.. however.02 M HF and 0. though some further calculations for the complexes should be performed.e. 7. for experiments conducted in M HF (where some hydrolyzed or partially fluorinated species are present). see Table 17. found in [172]. for the extraction of the positively charged complexes.1 M HF (no hydrolysis). where no hydrolysis should occur at such high acidities. Such an inversion of the trend is consistent with the theoretical trend for the formation of the species.

This sequence is in agreement with experiments on hydrolysis of Nb. The calculated relative of reaction (30) data are indicative of the following trend in are given in Table 18. Ta. The hydrolysis of group-5 cations: Nb > Ta > Db >> Pa. A simple model of hydrolysis [163] does not reproduce the difference between Nb and Ta having the same IR. Db and Pa) can be formed with different degrees of hydrolysis according to the following equilibrium To predict stability of those complexes. such as and (M = Nb. HCl and HBr solutions was studied theoretically [165. The data of Table 19 show the following trend in the complex formation of group-5 elements: Pa >> Nb > Db > Ta. Ta.2.166]. a large variety of complexes. The complex formation of group-5 elements in HF. Taking into account the work of transfer of the complexes between the phases. the following trend was predicted for the extraction of group-5 anions by an anion exchanger . As a result. the DFT calculations of the electro­ nic structures were performed for the above mentioned complexes of Nb. Db. Theoretical Chemistry of the Heaviest Elements 81 where M = Nb. Ta. and Pa. In HCl solutions. Db and Pa. The present model based on the real (relativistic) distribution of the electronic density does reproduce this difference. and Pa [163]. Ta. the for reaction (31) are given in Table 19. A motivation for this study was the unexpected behavior of Db (Ha at that time) in the extractions into triisooctyl amine (TIOA) from mixed HCl/HF solutions [176]: Db was extracted similarly to Pa and not to Ta.

W and Sg . [177]. a recommendation was made to conduct the AIX separations in pure HCl or HF solutions to try to observe the predicted sequence. Equation 32. The calculations also predicted the following sequence in the formation of various types of complexes as a function of the acid concentration: in full agreement with experimental results for Nb. Paulus et al. This non-tungsten-like behavior of Sg was tentatively attributed to its lower tendency to hydrolyze (deprotonate) compared to that of W. complexes of Pa should be formed in much more dilute HCl solutions. while much higher acid concentrations are needed to form complexes of Ta. That was the first time when predictions of extraction behavior of the heaviest elements based on quantum-chemical calculations were made. but came as a result of considering real chemical equilibria and calculating relativistically the electronic structure of the complexes. in contrast to Mo and W [178]. Accordingly.82 The Chemistry of Superheavy Elements Thus. and Br) as a function of the ligand L. which would have given a wrong trend.4 Element 106 Experiments on the CIX separations of element 106 from 0.1 M solutions showed that Sg did not elute from the CIX column. Ta and Pa turned out to be reversed in going to Db. the amine separations of the group-5 elements were systematically redone by W. The reversed has been established exactly as extraction sequence theoretically predicted. To interpret the behavior of Sg in these experiments and to predict its hydrolysis at various pH values. 7. This could not be predicted by any extrapolation of this property within the group.2. According to these results. Br in the formation of as the data of Table 20 show. and also confirmed by specially designed experiments. The calculations also reproduced the sequence F > Cl > (L = F. free energies of the following protonation reactions for Mo. The theoretical investigations have shown that the trend in the complex formation and extraction (Equation 32) known for Nb. Ta and Pa. Cl.

logK were determined for Sg. the trend is continued with Sg: Mo < W < Sg Thus. Theoretical Chemistry of the Heaviest Elements 83 were considered theoretically. The results shown in Table 21 indicate that for the first two protonation steps. the predicted trend Mo < W < Sg is in line with the experimental observations for Sg [178]. At low HF concentrations a reversal of trends occurs. Future experiments on the AIX separations of group-6 elements from HF solutions will clarify the position of Sg in this row. The obtained sequences are in agreement with experiment for Mo and W [180]. the same reversal in the trend is predicted for the protonation of oxyanions of the group-6 elements as that for the complex formation of the group-4 and 5 elements.2. . as given in Table 22 [167]. Complex formation of Mo. The predicted trends in the complex formation are in agreement with experiments for Mo and W at various pHs [163]. and Sg in HF solutions was studied theoretically [179] by considering the following step-wise fluorination process The calculated indicate a very complicated dependence of the complex formation on pH and the HF concentration. W. For the further protonation process.2. the trend in group-6 is reversed: Mo < Sg < W. while at high HF molarities the trend in continued with Sg: Mo < W < Sg.1. For the protonation/hydrolysis of positively charged complexes. Using the procedure described in Section 7. The for the consecutive protonation steps were calculated using the DFT method [167].

The curves for Tc and Re show peaks at about 7-8 M HCl associated with the reduction [182]. 7. complex formation and extraction of complexes at various experimental conditions in comparison with experimental results are summarized in Table 23. which means that Tc is less stable in the 7+ oxidation state (or more stable in the 4+ state) than Re. The stability of relative to could be established by AIX separations of group-7 elements in acidic solutions. In HCl solutions Tc and Re undergo the complexation reaction simultaneously with reduction. The peak for Tc is at lower HCl concentrations than that of Re indicating an earlier reduction of Tc. The position of the peak on the curve for Bh would.5 Summary of the aqueous chemistry studies Predicted trends in hydrolysis. It would also be interesting to conduct similar reduction experiments with Hs.4 PROSPECTS FOR AQUEOUS CHEMISTRY STUDIES From element 107 on. the maximum oxidation state is expected to be relatively unstable in solutions. be interesting to conduct experiments probing the stability of lower oxidation states.2.84 The Chemistry of Superheavy Elements 7. therefore. It would. therefore. be indicative of the relative stability of its 7+ oxidation state. Its homologues are known to have the following reduction potentials: of and .

element 114 would probably form or or by analogy with Pb. A tendency to form stronger bonding with “soft” ligands is foreseen in [12] by analogy with Hg showing increasing stability of the aqueous complexes from F to Cl to Br and to I (Table 24).33 kcal/mol as compared to the calculated -88. The stability of various complexes of element 114 versus stability of the hydrolysis products could be a subject of further theoretical investigations. see Table 24.2. Theoretical Chemistry of the Heaviest Elements 85 Element 112 should have an extensive complex ion chemistry. 0% (I) [183]. Thus. experiments could be conducted with probably only and The possibility of formation of and was also considered [108] (by analogy with Hg where the addition of an to or was found energetically favorable).08% (Br). the stability of the gas phase compounds of Pb decreases from F to Cl to Br and to I. As in group 12.4 kcal/mol for [108]. though in solutions this compound will undergo strong hydrolysis. another reason. . the existence of was suggested. taking into account the decreasing stability of the 2+ oxidation state in group 12. and (In 11 M HCl is known). like other elements at the second half of the 6d transition series. Thus. The increasing stability constants in this row has. however. the only or possibility would be the formation of Element 114 should also have a greater tendency to form complexes in solutions than Pb. while in aqueous solutions it is the other way around due to a decreasing hydrolysis from F to Cl to Br and to I (fluoride complexes are not known) according to the reaction or [184]. though these compounds will undergo strong hydrolysis in aqueous solutions and will not be stable.4% (Cl). 0. The formation enthalpy of was calculated at the PP level as -75. namely the decreasing hydrolysis Hg(OH)X : 1. The stability of the gas and crystal phase compounds of Hg decreases from F to Cl to Br and to I. Since the 2+ oxidation state of element 114 should be more stable than element 114 can be extracted as or In [107]. Since the stability of the 2+ state increases within group 14.

. stabilities of oxidation states. RECP were mostly applied to open-shell compounds at the end of the 6d series and the 7p series. Experimental results. so that relativistic calculations in the region of the heaviest elements are indispensable. embedded cluster calculations are under way. were helpful in defining the scope of the theoretical problems and provided an important input. Though substantial progress has been reached in understanding the chemistry of the heaviest elements. Very accurate fully relativistic DFB ab initio methods were used for calculations of the electronic structures of model systems to study relativistic and correlation effects. the RECP and DFT methods and their combination are the best way to study the theoretical chemistry of the heaviest elements. Presently. It was shown that relativistic effects play a dominant role in the electronic structures of the elements of the row and heavier. The Chemistry of Superheavy Elements Conclusions and Outlook Advances in relativistic quantum theory and computational methods made it possible to predict properties of the heaviest element compounds by performing accurate calculations of their electronic structures. These methods still need further development. crystalfield and SO effects. For the superactinides. The synergism between the theoretical and experimental research in the last decade led to better understanding the chemistry of these exotic species. Extensive DFT and PP calculations have permitted the establishment of important trends in chemical bonding. as well as the role and magnitude of relativistic effects. The molecular DFT calculations in combination with some physico-chemical models were successful in the application to systems and processes studied experimentally such as adsorption and extraction. since the resemblance of their properties to those of their lighter homologues will be much less pronounced. investigations of the chemical properties will be even more exciting. Straight-forward extrapolations of properties from lighter congeners may result in erroneous predictions. in turn. Relativistic atomic and molecular calculations in combination with various models were useful in helping to design sophisticated and expensive chemical experiments.86 8. as well as powerful supercomputers to be applied to heavy element systems in a routine manner. complexing ability and other properties of the heaviest elements. there is still a number of open questions needed to be answered from both the experimental and theoretical points of view. For theoretical studies of adsorption processes on the quantum-mechanical level.

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62. 62. 60. 47 Overlap populations (OP) 57. 60. 59. 61.2. 54 Ionization potentials (IR) 50. 61. 82 Element 107 (bohrium. 81 Element 106 (seaborgium. 41 Coupled cluster single-double excitations (CCSD) 41. 78 Element 105 (dubnium. 63 Element 104 (rutherfordium. 78 Dirac Slater discrete variational (DS-DV) method 44. 63 Polarizability PP CCSD Pseudo potentials (PP) 54 69 42 Cation exchange separations (CIX) 80 Complex formation 77 Configuration interaction (CI) 40 Correlation effects 32. 47 Density Functional Theory (DFT) 43.. 86 Adsorption enthalpy 64. 83. 52 Lamb-shift 38 Local density approximation (LDA) 44 Lowest unoccupied MO (LUMO) 56 Molecule-slab interaction 66 Mulliken population analysis. 38. 55. 84 Breit effects 38 Element 114 Element 118 Generalized gradient approximation (RGGA) 73 74 44 Highest occupied MO (HOMO)55 Hydrolysis 77. Db) 55. 68 Coupled cluster (CC) 33. 43. 53. 82. 45. 40. 59. 56. 70. Bh) 60 Element 108 (hassium. 63. Theoretical Chemistry of the Heaviest Elements Index 93 Ab initio methods 41. 41. 46. 46. Rf) 55. 51. 67 Amsterdam density-functional (ADF) method 45 Anion exchange separations (AIX) 80. 41. 58. 40. 70 Multiconfiguration Dirac-Fock (MCDF) 40. 76 Relativistic effect (indirect) 36 Relativistic effective core potentials (RECP) 42 . 36 Effective charges 57. Hs) 61 Element 111 68 Element 112 70 Quantum electrodynamic (QED) effects 38 Quasirelativistic (QR) PP 43 RECP-CCSD(T) 59 Redox potential 75. 78 Dirac-Coulomb-Breit (DCB) Hamiltonian 39 Dirac-Fock (DF) 33 Dirac-Fock-Slater (DFS) 33 Direct relativistic effect 35. 42. 83 Intermetallic compounds 70 Ionic radius (IR) 51. Sg) 55. 66. 53.

74 64. 66 45 Spin-orbit (SO) splitting Thermochemical stability Transactinide elements 37. 65.94 The Chemistry of Superheavy Elements Van der Waals bond Volatility ZORA method 54. 38 55 34 .

Such extreme conditions represent a huge experimental challenge for radiochemists [1. Radiochimie. 95-116. ultra-traces and for a single atom ? The tracer scale covers usually element concentrations ranging from to M [2]. France 1. therefore.2.). the knowledge of Z is not sufficient to predict its chemical behavior: the expected occurrence of relativistic effects (see V. Introduction The discovery of a new transactinide or superheavy element (SHE) is based on the identification of the atomic and mass number of the produced isotope. © 2003 Kluwer Academic Publishers.3]. Le Naour Institut de Physique Nucléaire. Thus. the number of entities present in 95 M. are essential.Chapter 3 Fundamental Aspects of Single Atom Chemistry D. chemical experiments have to be conducted with a few atoms or even a single atom. Trubert and C. Schädel (ed. SHE have short half-lives and low production rates. Experiments. The question is whether the concepts of thermodynamics and kinetics used in classical chemistry are relevant at tracer scale. The Chemistry of Superheavy Elements. . F-91406 Orsay Cedex. the chemical behavior of transactinide elements cannot be extrapolated straightforward from the properties of their lighter chemical homologues. At such low concentrations. Printed in the Netherlands. to assess the chemical properties and therefore the place of the element in the periodic table. Pershina in Chapter 2) may lead to deviations in the regularity of the periodic table. However.

the fundamental microscopic and macroscopic concepts of the thermodynamics. cannot be applied directly: i) Macroscopically. as they constituted the general case for SHE chemistry. Thus. for example as a result of the different degrees of consumption of ligands leading to unusual complexation reactions or in unexpected redox processes [4]. is perfectly valid. involving true homogeneous solution without pseudo-colloids [2]. they will not be taken into account in the fundamental (thermodynamics and kinetics) concepts. Tracer scale chemistry is also characterized by a kinetics hindrance for reactions between two microcomponents in a given system: this trend excludes polymerization reactions or disproportionation for ultra trace chemistry. Since edge effects are difficult to quantify. Thermodynamics at Extreme Dilution and for a Single Atom When the number of atoms decreases to a few tens of atoms and a fortiori to one atom. obviously as far as the relevant reaction is kinetically allowed. In ultra diluted systems. when the number of . The aim of the present chapter is to describe what happens when the concentration of the microcomponent decreases to some tens of atoms and finally to the ultimate limit of dilution: a single atom. the basic notion of phases disappears since the repartition of the entities becomes less homogeneous. Only aqueous chemistry will be evoked. the second deals with kinetic aspects and one-atom-at-a-time chemistry. only reactions of a microcomponent with macrocomponent will be treated. some discrepancies can occur in particular cases. valid at tracer level. Consequently. Then. 2. the Stirling approximation (Equation 1) used for the calculation of the free enthalpy of the microcomponent in the gaseous phase and therefore in the derivation of the thermodynamic activity in a condensed phase.96 The Chemistry of Superheavy Elements lies between and This number is large enough to apply the mass action law without any restriction. experimental approaches and finally effects of the media and their influence on aqueous chemistry will be discussed. This chapter is divided in four parts. the behavior of the microcomponent is expected to be the same at normal concentration and at the tracer scale. In the following considerations. However. because the mass action law applies. micro-microcomponent reaction will be evoked in Section 3. The first one is devoted to thermodynamic considerations. Experimental limits of the system (container) are always finite. the thermodynamical behavior of an element does not depend on concentrations.

V. it is assumed that the reactional volume is small enough and that the time devoted to the reaction is larger than the time required for establishment of equilibrium. only the reactions where the stoichiometric coefficient of the microcomponent (m) is equal to unity will be examined. the application of statistical mechanics in kinetics will not be demonstrated in this chapter. with only a few atoms the probability of an encounter between two microcomponents is infinitely low. ii) From the microscopic point of view. V. reactions involving the formation of polynuclear compounds are excluded. . In the following. The reaction can be written in the general form: Where are the stoichiometric coefficients (positive for adducts and denotes the macrocomponent. All the following considerations refer to pure thermodynamics (phenomenologic.3. Therefore in the following discussion. These aspects will be described in Section 3. Therefore. The definition of the partition coefficient must also be revised since at the extreme limit of a single atom. Fundamental Aspects of Single Atom Chemistry 97 atoms decreases. to access thermodynamic values. classic and statistic) and do not take into account kinetic aspects of the equilibrium. Moreover. However. the Stirling equation can not be used to calculate the factorial factors included in the partition function Z(T. this latter can only be in one phase at a time. it is necessary to substitute the concept of a time-independent statistical ensemble by the concept of a time dependant statistical behavior of elementary entities. The negative for products) and corresponding mass action law is obviously: Where K is the equilibrium constant and is the thermodynamical activity of each entity (macro and microcomponent) involved in the equilibrium. of the entities Moreover. derivation of the partition function with respect to can not be performed in order to determine Z(T. It should be noted that statistical mechanics offer a powerful tool for mathematical treatment of both thermodynamics and kinetics. Equation 3 can also be expressed in terms of concentrations (corrected with activity coefficients). the free enthalpy of the entities This means that the equilibrium between and the other entities of the system cannot be described as usually by using the chemical potentials of Therefore. the number of entities cannot be considered as a continuous variable.

Z is the partition function of all species. the thermodynamical values of the system S are related to the mean values of the number of entities Where P(N) is the canonical probability of realization of the states of the closed system which constitutes this phase. one has to establish first. Only the equations necessary for the basic understanding of the demonstration are presented in this paragraph. It is also assumed that a dynamic equilibrium is achieved. the thermodynamical relations with some tens or hundreds of atoms and then extrapolate these concepts to a single atom. let be the ratio of these two quantities: This expression of P(N) (Equation 5) allows to calculate for every case the and K. In order to compare the expression of the mass action law for microcomponent and macrocomponent (in the former case activities can be replaced by concentrations). The probability P(N) is defined from all the partition functions of the included entities: Where is the partition function of all species and whose numbers are far above hundreds and the Z(T. of phase volume V and temperature T. which is the only case encountered in transactinide chemistry.V. Details of the mathematical treatment can be found in Appendix 1. we will focus on the case of a single microcomponent involved in a reaction of stoichiometry 1-1. S(T.N). According to statistical concentration thermodynamics. the entities Ei(mj) have time to occupy the quantum states of the system S.N) is partition function for species whose number is less than 100.98 The Chemistry of Superheavy Elements Before dealing with the ultimate case of single atom chemistry. and thus acts as a normalization factor. containing N entities included in only one type of molecule.V. From the general equations of P and Z. This condition is fulfilled since generally the residing times are very short. The Equation 2 reduces to: .e. in a system. values of and from the known values of All these considerations assume that the element is stable or has a half-life large enough to allow the occupation of all the quantum states corresponding to the different degrees of freedom of each entity (m). i. In the case of a small number of entities the notion of a mean must be introduced.

the initial numbers of and in presence when i = 0. . if the mean concentrations are used. Fundamental Aspects of Single Atom Chemistry 99 Let i be the extent of the reaction. Down to the case of a single atom that can only appear in one species at a time. regardless of the number of present species. When the extent of the reaction is i species considered as the product of the reaction and species that coexist together with other species. according to the general expression P(N). can be defined as : After rearrangement and normalization (Appendix 1). Equation 9 becomes: When and increase. the situation of the classical equilibrium is reached for which the most probable canonical state is that of the highest P(i). in the case of a reaction of stoichiometry 1-1. the mass action law holds. the probability becomes: . The successive values of P(i) and P(i)-1 come closer and closer and the limiting value of the ratio given by Equation 10 is unity. The canonical probability for realizing of the micro-states of the system. Where is a coefficient characteristic of E(m) for the system S which depends only on the macrocomponents is equal to unity for an ideal gaseous phase) [5]: The parameter . see Appendix 1. Then: It becomes: Thus.3. turns to P(i). and only in this case. characteristic of the system.

P. Obviously.100 The Chemistry of Superheavy Elements is While the probability of the single atom into another species Based on the above.7]. the mass action law can be used with the mean concentrations proportional to and The case of a microcomponent with a reaction of stoichiometry (different from 1-1) is much more complicated.4]: It can be seen immediately that a decrease of the concentration of the species and results in an increase of in the same proportions. the concentration of and With these assumptions. As a first approximation. a decrease in the rate constant would yield much higher reaction times (exponential). Guillaumont and J. a macroscopic model of activated complex is based on the free energy of activation of the system and especially on the collision frequency between reactants [6. The ratio is a function of and K. the half-time of the reaction is simply [2. It will be discussed whether the notion of half-time associated with such a reaction is valid (Equation 16) in ultra trace chemistry. assuming a very fast reaction rate the half-time is equal to and 1. which means that deviation from the law of mass action can occur. 3. respectively. for a single atom and in the case of a reaction of stoichiometry 1-1. for 100 atoms of plutonium. R. The half-time of the reaction is determined by the concentrations of the and and the rate constant and The general case with species leads to a rather complicated expression of A and hypothesis must be introduced to simplify the equation: at time zero the concentrations of and are nil. stoichiometric coefficients will be taken as unity. Diffusion phenomena have negligible effects since for a typical coefficient . Assuming a general reaction of two entities containing a microcomponent: and being the forward and the backward kinetic constant of the equilibrium. Adloff [4] have shown. Kinetic Aspects The kinetics at extreme dilution between two microcomponents is strongly hindered. For sake of simplification. Thus.6 y in a volume of and respectively. there is no general solution to describe the variations of with and each particular case needs to seek its own solution.

. The rate of the reaction of species E containing .J. Without presenting the mathematical treatment [7]. are much simpler. As there is no consumption of the macrocomponent. combined with the frequency of exchange between entities.e. Applying a Maxwell-Boltzmann distribution requires that an individual atom or species can acquire energies levels quite different from its most probable or mean values [7]. The aspects of kinetics of a reaction between a microcomponent with a macrocomponent. This fundamental concept forms the basis of the fluctuation theory. takes the form: the microcomponent with macrocomponent Since all terms on the right side of Equation 18.7]: property of a system . it can be seen that the reaction rate of a given number of atoms of a micro component decreases drastically with the spatial expansion of the system in which they are contained (i. Their approach was based on activation energy (activated complex). which is far greater than the exchange frequency required to establish an equilibrium.J. Therefore. classical or formal thermodynamics and kinetics never take fluctuations into account. including macrocomponent concentrations.3. Borg and G. the only kinetics data that can be reached at extreme dilution are those related to reactions between the microcomponent and a macrocomponent. Equation 18 becomes: Where k’ becomes a “conditional” rate constant of the “pseudo” first order [8]. Summarizing.. However. kinetics appears of the “pseudo” first order with respect to the microcomponent [2. Hence. This approach has led to the conclusion that the equilibrium cannot be reached if the activation energy is greater than about 85 kJ. Fundamental Aspects of Single Atom Chemistry 101 value of diffusive displacements occur per second. R. Energies of activated complexes can only be used for sufficiently high quantities since this concept involves energies estimated from statistical values. the relative mean deflection of a can be estimated according to [6. Dienes [9] have attempted to show the validity of single atom chemistry from a kinetics point of view. remain constant under the given conditions. the concepts developed in Borg’s work are only valid for large number of atoms. the number of atoms per volume unit). However. at critical concentrations.8]. micro-microcomponent kinetics prevails largely over thermodynamics in a reaction.

if the atom is stable or has a large half-life. Therefore. From a theoretical point of view. the single atom was assumed to be stable. any radiochemical techniques can be used for single atom chemistry. An “observable” chemical reaction of a given radio nuclide can be defined with the following temporal quantities: half-life of the radionuclide t: time necessary for reactants to compete half-time of equilibrium or steady state chemical reaction time for collecting data A reaction will be observable if: At the experimental scale. However. In fact. Note that reactions with a 1:1 stoichiometry include all reactions between the microcomponent and a single macrocomponent. and t are macroscopically related. for a 1:1 stoichiometry reaction the mass action law and the kinetics laws are valid. This concept can also be extended to stepwise reactions such as successive formation of metal complexes (hydrolysis. such reaction appears as of pseudo first order. considered in this chapter. an understanding of the decay appears rather important in one-atom-at-a-time chemistry [2. Problems associated with the disintegration of a single radioactive atom will not be developed here However. The interested reader can find a brief development of this concept in Appendix 2.102 The Chemistry of Superheavy Elements N is the number of atoms or species. The concept of “one-atom-at-a-time chemistry” is different from that of a single atom chemistry. The main difference is the time. the probability for a unique atom to exist in specific “specie” can only be determined in a chemical experiment if the atom is radioactive. halide complexation). one may ask if it is meaningful to carry out experiments with a single atom. For the development of concepts of kinetics and of thermodynamics. Conclusive Remarks on Fundamental Aspects of Single Atom Chemistry Since the SHE chemistry is correlated with one-atom-at-a-time chemistry. the fluctuation has the same order of magnitude as the property itself. 4. Therefore for a single atom. as it was demonstrated above.10]. for example: . as there is no macrocomponent consumption.

Thus. In principle. All these effects. As only ideal system were considered. radiochemists who intend to perform experiments at the scale of one atom must be aware that the presence of any solid phase (walls of capillary tubes. where the radioactivity measurement is the only way to detect the element (but it does not allow the identification of the form of the species). these concepts are not longer valid. So far. In the case of radioactive tracer. redox processes with impurities or surfaces. The following section describes experimental techniques used in SHE chemistry. two types of external perturbation can be applied: (i) by contacting the system with a second phase and subsequently observing the distribution of the radio­ nuclides between the two phases (static or dynamic partition) or (ii) by applying an electrical potential or a chemical gradient (transport methods). Experimental Approaches Each study of the chemical property of a transactinide element requires the development of radiochemical technique that allows collecting data relevant to the scale of one atom.) can perturb the experimental system. 5.3. sorption phenomena. etc. However. vessels. an external perturbation must be applied to the system and its response must be analyzed. medium effects have not been taken into account. and each case becomes a particular case seeking its own solution. have finite dimensions (time and volume). transport methods have not yet been used in one-atom-at-a-time . edge effects. both for thermodynamics and for kinetics. chemical information on a system can only be obtained with methods that do not alter the species present in solution. in order to get this information. It should be pointed out however that in practice. pseudo-colloid formation. all the studied systems. cannot be predicted with formal thermodynamics and/or kinetics. Fundamental Aspects of Single Atom Chemistry 103 For higher stoichiometry. especially in SHE chemistry. Experimental approaches are therefore severely limited. It is important to check that these edge effects are negligible at tracer level before performing experiments at the scale of the atom [11]. representing the most important part from the deviation to ideality. All the previous theoretical considerations have been established assuming an “ideal system” without any boundary conditions.

ligand concentrations. [12] using a mixture . Although partition methods are widely used in the field of radiochemistry. On line experiments with short lived isotopes of homologues are also necessary to improve the setup. to evaluate the eventual impact of edge effects (sorption.. Obviously for a single atom. . measurements of average concentrations of the entities present in each phase have to be performed. solvent extraction was the most used for heavy elements studies. The experimental conditions must always ensure that at the end of the experiment. etc). regardless of the concentration involved. chemical properties can only be determined through the variations of D with characteristic parameters of the system (ionic strength.. the short half-life of the nucleus does not bring any perturbation since there is only one alternative: either the measurement indicates in which phase the atom is or the atom has disintegrated before the measurement and no information is obtained.104 The Chemistry of Superheavy Elements chemistry since they are not only difficult to carry out but also extremely time consuming. under given conditions. temperature. the determination of one partition coefficient (D) requires numerous repetitive experiments. The aim of a partition experiment. acidity. ion exchanger. Prior to experiments with SHE.g. the atom has reached permanent partition equilibrium between the two phases.. the distribution coefficient is defined in terms of a probability for the element to be in one phase or in the other.. Moreover. . Among the static partition techniques. This means that measurements must be conducted with the whole phase since the system contains only one entity. even for the more simple case involving only one chemical species in each phase. the accuracy in the measurement of the average concentrations increases with the number of trials. For a given system. on line experiments involving SHE may preferably be performed with homologues since it is the only way to ensure strictly identical experimental conditions for all present elements. In the case of a few atoms. Since this procedure is sequential. e. For instance R. the atom (necessarily radioactive in the present context) is distributed between two immiscible phases (liquid and/or solid). For this purpose.1 STATIC PARTITION In a static partition. it has been shown that the law of mass action involves probabilities for the atom to form a given species in a given phase.J. 5. Furthermore. aqueous media.).). Silva et al. systematic studies with homologues at the tracer scale have to be carried out to select the experimental conditions (solvent extraction. is the determination of the partition coefficient (D) of an element between two phases.

the same conclusion concerning “coprecipitation reactions” cannot be drawn system­ atically. Czerwinski et al. of which only a tenth remained for detection at the end of the experiment. [14]. 15]. have to be considered with caution since the experimental conditions have not been maintained identical i. adsorption (chemisorption. In case of sorption. In view of the numerous experimental conditions to reproduce and to parameterize. F. results of K. it did not allow determining a reliable D value. ii) Hf was studied on line with experimental procedures different from the batch ones (volume. stirring mode)... is strongly correlated with the pH. iii) in the Rf study only the organic phase was analyzed. the isoelectric point of the solid [16]. [13] regarding extraction of Rf and homologues in HCl media with TBP. Fundamental Aspects of Single Atom Chemistry 105 of TTA / MIBK have demonstrated the 3+ and 2+ oxidation state for Lr and No respectively. When dealing with a few atoms. allowing therefore the collection of information on the chemical properties of a microcomponent. even if a multi-step mechanism (frequent and rapid sorption – desorption steps) is involved. Although no evidence for a concentration-dependent behavior of Po was observed.3. A statistically reliable result was obtained by performing about 200 identical partition experiments. which is in contradiction with the basic principle mentioned above. coprecipitation – even if the mechanism remains unknown -.: i) Hf was not included in the batch experiments. The previously observed low extraction yield was correlated with sorption of Hf. The low D value of Hf obtained in Czerwinski’s work was not confirmed by C. Reischmann et al. syncrystallization is strongly hindered. D.18] have studied the influence of concentration to 40 atoms) on “coprecipitation ” with tellurium and arsenic sulphide.e. Conversely. In a single experiment. at tracer level. The term “coprecipitation” has no precise meaning since it involves many phenomena as syncrystallization (homogeneous incorporation of a microcomponent in the lattice of an isomorphous macro-compound).is a convenient method for the separation or concentration of different species.. no chemical information can be derived from these experiments. a sample of about 10 atoms was available. Kacher et al. [17.J. These factors are related to the properties of the solid (surface charge. grain size) and of the electrolyte solution (ion nature. proton concentration. electrostatic adsorption) and surface precipitation [2. that determines the sorption properties. a distribution coefficient can hardly be formulated [2]. However. this technique depends strongly on to many experimental parameters to allow reproducible results. If solvent extraction and ion exchange batch experiments are commonly considered as multi-step procedures. The variety of experimental conditions does not ensure the absence of edge effect and as the aqueous phase was not measured in this Rf experiments. The coprecipitation of carrier free Tc and Re with .R.): especially. contact times.

The validity of these experiments has been checked previously with systematic studies on homologues off line and simultaneously on line with Rf. To go further in this topic.. the atom can be observed in a well-defined elution fraction. .106 The Chemistry of Superheavy Elements in media was used successfully as an additional separation step of these group 7 elements from Nb and Ta [19]. elution chromatography and thermochromatography (out of the scope of this chapter – see Chapter 7). were able to demonstrate. 5. but also the behavior of homologues in batch and on line which dynamic partitions are performed . In solution chromatography. using the HPLC setup of ARCA II. by the same constant K. The first significant experiments on the behavior of SHE in aqueous solutions were performed in order to collect comparative data between SHE species and actinides or/and homologues. using extraction chromatography. With elution chromatography. Distribution coefficients of Rf [22. Techniques . Ta and Pa. the precipitate was used to prepare an alpha source. From their results. validating therefore the method used and the conclusions drawn on the chemical behavior of SHE. the similarity of chloro-complexes of Hf and Rf. ensuring identical experimental conditions. In a single experiment. are particularly suitable for one-atom-at-a-time chemistry. [21] unambiguously showed the stability of the 5+ oxidation state of dubnium similar to Nb. and their difference from the trivalent actinides Cm and Fm [20]. At the same time.2 DYNAMIC PARTITION A dynamic partition can be considered as a succession of static partitions. governed as a first approximation. For instance. no concentration-dependant behavior was observed. based on the detection of 6 events. 23] in HF/HNO3 media and HF/HC1 [24] were determined from ion exchange experiments. extensive research was conducted using the same chemical techniques in order to get quantitative data. The feasibility of determination in the context of one-atom-at-a-time values will allow to chemistry is very promising since the collection of establish reliable variations of the chemical properties (complexation. a significant result can be obtained since it is in its own purely statistical. implying that the position of the elution band can be determined with a single atom. Schädel et al.K.such as extraction (reverse phase) chromatography. E. In this type of experiments. In other words such partition is characterized by a large number of successive equilibria. controlled by K. These two illustrative works concern not only the SHE at the atom scale. Hulet et al. is directly related to the probability of the presence of the atom in the mobile phase. the displacement of the species. M. and unlike group-4 elements and trivalent actinides.

30]. an extra­ polation to zero ionic strength remains the only universal thermodynamical value for a given equilibrium. All thermodynamical laws are valid and must be applied without restrictions. Such deviations have been described in the literature by numerous models. Since it is independent of the nature of the supporting electrolyte. The purpose of this paragraph is to remind the reader that the effects of media govern the reaction constants not only in pure aqueous solutions but also in partition experiments [28. Fundamental Aspects of Single Atom Chemistry 107 hydrolysis) of elements within a group. The microcomponent does not act in the Coulomb forces between charged ions calculations of the ionic strength mainly impose deviation of experimental constants from zero ionic strength under well-defined conditions. The effects of the media are imposed by macrocomponents and by support­ ing electrolytes if present. However.31]. which will not be reiterated here [29. which offers the advantages of using simple equations and takes into account the possible dissymmetry of elution bands [25. Unfortunately. Neck et al. [32] to estimate successive hydrolysis constants using the inter-ligand electrostatic .3. to compare with theoretical predictions. The mathematical treatment of elution curves can be carried out with various models. sometimes difficult to determine and/or to estimate. These effects were often ignored in a large number of papers in the past. Temperature effects will not be treated here. Medium Effects The media used in aqueous chemistry have a huge influence on the reaction thermodynamics and must be taken into account. Recently a model was proposed by V.29. these types of experiments are very cumbersome and have never been carried out with heavy elements. and to determine perhaps thermodynamic constants. 6. A systematic study of the width of the elution band as a function of elution rate is required to determine the variations of EHTP. The parameters included in Glückauf’s equations allow the determination of the distribution coefficient and possibly of the diffusion coefficient of the species in the mobile phase through the knowledge of the effective height of theoretical plate (EHTP) [27]. Moreover. especially Glückauf’s. For high concentrations. they could bring information about the diffusion constant and the related Stoke’s radius of the species in solution [26. This latter parameter is characteristic of the efficiency of the column. but they are of significant importance [29]. such extrapolation requires the knowledge of numerous parameters. other information could be derived from chromatography experiments. neutral species and multiple interactions between species must also be taken into account.26]. However.27].

From Sergievskii’s model indeed. However. they can be estimated from the model developed by L. But.D. [13]. essentially because of medium effects. U. Therefore. the activity coefficient of a species in the organic phase depends only on the water activity of the bi-phasic system [28]. must be considered with caution.108 The Chemistry of Superheavy Elements repulsion term. maintaining the water activity constant (or the ionic strength) does not neutralize all causes of deviations from an ideal solution. [14]. even if the methodology used by the latter would be adequate (which is not the case – see above). At higher electrolyte concentrations. a direct comparison of results issued from different chemical procedures is delicate. paradoxically for actinide ions such data are relatively well known. Except for some recent work. available in the literature at various ionic strengths. Ciaviatta [33.R. MSA. … [29. This model gave accurate results for actinides (Th. A system involving liquid-liquid partition can be perfectly defined in thermodynamical terms. Even in one-atom-at-a-time experiments involving the same aqueous media. they involve a larger number of characteristic parameters. Most of these constants were determined with weighable amount of elements.31]) have been developed. R. and approximately below 3 mol the Specific Ion interaction Theory (SIT) [29] can be applied for the calculations of activity coefficients.34]. in certain cases. the influence of the aqueous phase on the activity coefficients in the organic phase is also constant. Part of their discussion is devoted to a comparison with the work of K. Nevertheless. The knowledge of both thermodynamic constants at zero ionic strength and of the specific interaction coefficients will allow the speciation diagram of the element in the considered medium to be established. In extraction . [35] have reinvestigated the behavior of Rf and homologues in the system HCl/TBP using solvent extraction and extraction chromatography. In their work. In batch experiments they obtained similar results as those of C. Zr and Hf are reliable since no edge effects have been proved to occur. However. A comparison of hydrolysis or complexation constants of homologues. In case of low charged species. data collected in liquid-liquid solvent extraction and extraction chromatography cannot be directly compared. Np and Pu) and can be extrapolated to other complexation reactions as long as data are available on chemical homologues. Kacher et al. which unfortunately are unknown for the majority of chemical elements. most data on SHE chemistry were determined in concentrated media with sometimes undefined ionic strength. more sophisticated theories (Pitzer. However. Czerwinski et al. Their on line experiments with Rf. Günther et al. Data available on interaction coefficients are scarce. if the water activity of the system is kept constant.

This leads to meaningful thermodynamic data such as the recently determined value of Rf [22.V. the water activity cannot rigorously be defined and maintained constant [28]. The collection of experimental data must also include effects of the media and the temperature (if used). only valid if has an integer value. mean values are not only integers. which corresponds to usual concentrations. the variations of the water activity in both phases can be neglected.3. at low ionic strength.24]. the partition function of S becomes that of a canonical ensemble without mean values: . For large values of Equation 22 becomes: Equation 23 is a form of the Stirling equation. 7. Reactions between a microcomponent and macrocomponent are always allowed kinetically. the absence of edge effects must be checked carefully at the tracer scale.1) being the molecular partition function.23. However. at extreme dilution. Appendix 1 The mean number of entity system S is given by: and the mean partition function of a Z(T. Fundamental Aspects of Single Atom Chemistry 109 chromatography (or reversed phase chromatography) and in ion exchange chromatography. Obviously. the mass action law can be applied with mean concentrations proportional to the probabilities of finding an atom in one species or another. this derivation of the mass action law can only be achieved for reactions with a 1-1 stoichiometry. the rate of the reaction being of the “pseudo” first order. Conclusion In the case of a single atom. limitations are mainly imposed by the one-atom-at-a-time concept since the time devoted to the collection of data may be important. Prior to experiments to be carried out at the level of a single atom. But. Experimentally. the kinetics of reactions involving two microcomponents is strongly hindered. In this case. However.

P(N) is defined from all the partition functions of the included entities. the presence of some species E(m) of a microcomponent in a defined phase does not perturb the system. Comparing the expression of the mass action law for microcomponent and macrocomponent (in the former case activities can be replaced by concentrations). then: Where P(N) is the canonical probability of realization of the states of the closed system which constitutes this phase. of a single species E(m) in Introducing the partition function.V. Then. the ratio of these two quantities is defined as To establish the expressions of K and one must know the expression of the canonical probability P(N) in order to determine the mean values In a well defined closed system S(T. the properties of the system are only fixed by the amount of the mac­ rocomponent and then the energy levels of a single entity E(m) are given by: Where and are the energy levels in an ideal system and an additional term only dependent of the whole properties of the phase.N). when has a small value. The molecular partition function becomes: Where is the Boltzmann constant.110 The Chemistry of Superheavy Elements Back to the mean values of the number of entities. only the mean values of the concentrations are relevant to describe the system. a coefficient characteristic of E(m) for the system S an ideal system and is equal to unity for an which depends only on the macrocomponents ideal gaseous phase) [5]: . respectively.

The probability P(N) is then given by: Z is the partition function of all the species. For the sake of simplification of Equation 8.3. Equation 35 turns to: . let pose Equation 8 becomes: for i = 0.N) for species whose number is less than 100. and therefore: Setting: being a parameter characteristic of the system.V. Fundamental Aspects of Single Atom Chemistry 111 And Therefore. and acts as a normalization factor. the partition function for the species E(m) is: For several i species for j elements: This expression of the law of the realization of the microscopic states can be separated in two parts: the partition function of all species and of which numbers are far above hundreds and the partition function Z(T.

respectively. that describes successfully experimental data for a large number of bimolecular reactions. that can be estimated according to: represents the number of closely spaced energy levels and N the Avogadro number. The final transformation of the activated complex AB* in product (C) is governed by oscillations of low frequencies [6]. the properties of the systems can be calculated in the most probable state. Based on the molecular collision model.112 The Chemistry of Superheavy Elements then it The K* value is obtained by normalizing P(i) from follows: The average values of and are given by: Appendix 2 The transition state model considers a chemical reaction as an equilibrium between the ground state of the reactants and their state on the top of the potential barrier of reaction (activated complex) [6. as it can be seen in Equation 41.7]. The interested reader can find details of these theories and further considerations in references [6. the rate of the reaction can be calculated as the number of collisions of molecules having energy higher than the required value E* [7]: Where is the reduced mass and the radii of the molecules A and B. As quoted in Section 3 of the present chapter.7]. When the atom number is large enough (at least some hundred of atoms). the . Moreover. the reaction rate is strongly dependent of the height on the potential barrier E*. a chemical reaction can be described as a stochastic process of molecules crossing a potential barrier through many quantum excitations [7]. fluctuations represent one of the most fundamental concepts of statistical mechanics and/or thermodynamics (not included in traditional thermodynamics). Within this model. Therefore.

3. Fundamental Aspects of Single Atom Chemistry


relative mean deflection of a property of a system according to [6,7]:

can be estimated

Where N is the number of atoms or species. Thus for a single atom, the fluctuations have the same order of magnitude than the property itself and formal statistical mechanics equation cannot be applied.


The Chemistry of Superheavy Elements

1. 2. 3.

4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14.

15. 16. 17. 18. 19. 20. 21.


23. 24.


Hoffman, D.C.: Radiochim. Acta 61, (1993) 123. Adloff, J.P., Guillaumont, R., Fundamentals of Radiochemistry, CRC Press, Boca Raton, 1993. Kratz, J.V.: “Chemical properties of the Transactinide Elements”. In: Heavy Elements and Related New Phenomena, Eds. Greiner, W., Gupta, R.K., World Scientific, Singapore, (1999) 129-193. Guillaumont, R., Adloff, J.P.: Radiochim. Acta 58/59, (1992) 53. Guillaumont, R., Adloff, J.P., Peneloux, A., Delamoye, P.: Radiochim. Acta 54, (1991) 1. Liboff, R.L., Introduction to the theory of kinetic equations, John Wiley & sons, New York, 1969. Koudriavtsev, A.B., Jameson, R.F. and Linert, W., The law of Mass Action, Springer-Verlag, Berlin, 2001. Guillaumont, R., Adloff, J.P., Peneloux, A.: Radiochim. Acta 46, (1989) 169. Borg, R.J., Dienes, G.J.: J. Inorg. Nucl. Chem. 43, (1981) 1129. Schmidt, K.H., Sahm, C.C., Pielenz, K., Clerc, H.G.: Z. Phys. A 316, (1984) 19. Guillaumont, R., Bouissieres, G.: Bull. Soc. Chim. France 12, (1972) 4555. Silva, R., Sikkeland, T., Nurmia, M., Ghiorso A.: Inorg. Nucl. Chem. Letters 6, (1970) 733. Czerwinski, K.R., Kacher, C.D., Gregorich, K.E., Hamilton, T.M., Hannink, N.J., Kadkhodayan, B.A., Kreek, S.A., Lee, D.M., Nurmia, M.J., Türler, A., Seaborg, G.T., Hoffman, D.C.: Radiochim. Acta 64, (1994) 29. Kacher, C.D., Gregorich, K.E., Lee, D.M., Watanabe, Y., Kadkhodayan, B.A., Wierczinski, B., Lane, M.R., Sylwester, E.R., Keeney, D.A., Hendricks, M., Stoyer, N.J., Yang, J., Hsu, M., Hoffman, D.C., Bilewicz, A.: Radiochim. Acta 75, (1996) 127. Benes, P. and Majer, V., Trace chemistry of aqueous solutions, Elsevier, Amsterdam, 1980. Stumm, W.: Chemistry of the Solid-Water Interface, Wiley Interscience Publication, New York, 1992. Reischmann, F.J., Trautmann, N., Herrmann, G.: Radiochim. Acta 36, (1984) 139. Reischmann, F. J., Rumler, B., Trautmann, N. Herrmann, G.: Radiochim. Acta 39, (1986) 185. Schumann, D., Novgorodov, A.F., Misiak, R., Wunderlich, G.: Radiochim. Acta 87, (1999) 7. Hulet, E.K., Lougheed, R.W., Wild, J.F., Nitschke, J.M., Ghiorso, A.: J. Inorg. Nucl. Chem. 42, (1980) 79. Schädel, M., Brüchle, W., Schimpf, E., Zimmermann, H.P., Gober, M.K., Kratz, J. V., Trautmann, N., Gäggeler, H., Jost, D., Kovacs, J., Scherer, U.W., Weber, A., Gregorich, K.E., Türler, A., Czerwinski, K.R., Hannink, N.J., Kadkhodayan, B.A., Lee, D.M., Nurmia, M.J., Hoffman, D.C.: Radiochim. Acta 57, (1992) 85. Strub, E., Kratz, J.V., Kronenberg, A., Nähler, A., Thörle, P., Zauner, S., Brüchle, W., Jäger, E., Schädel, M., Schausten, B., Schimpf, E., Li Zongwei, Kirbach, U., Schumann, D., Jost, D.T., Türler, A., Assai, M., Nagame, Y., Sakama, M., Tsukada, K., Gäggeler, H.W., Glatz, J.P.: Radiochim. Acta 88, (2000) 265 Pfrepper, G., Pfrepper, R., Krauss, D., Yakushev, A.B., Timokhin, S.N., Zvara I.: Radiochim. Acta 80, (1998) 7 Trubert, D., Le Naour, C., Hussonnois, M., Brillard, L., Monroy Guzman, F., Le Du, J.F., Constantinescu, M., Barci, V., Weiss, B., Gasparo, J., Ardisson G. : Extended abstracts. 1 St International Conference on the Chemistry and Physics of the Transactinide Elements, Seeheim, September 26-30 (1999). Contribution PW-20 Glückauf, E.: Trans. Faraday Soc. 51, (1955) 34.

3. Fundamental Aspects of Single Atom Chemistry


26. Glückauf, E.: “Ion exchange and its application”, Society of Chemical Industry, London, 1955. 27. Helferich, F.: “Ion exchange”, Mc Graw-Hill, New York, 1962. 28. Marcus, Y. and Kertes, A.S., Ion exchange and solvent extraction of metal complexes, Wiley-interscience, London, 1970. 29. Grenthe, I., Puigdomenech, I. (Editors), Modeling in aquatic chemistry, OECD/NEA, Paris (France), 1997. 30. Duplessis, J., Guillaumont, R.: Radiochem. Radioanal. Letters 31, (1977) 283. 31. Barthel, J.M.G., Krienke, H., Kunz, W.: Physical chemistry of electrolyte solutions modern Aspects, Springer-Verlag, Steinkopff Darmstadt, 1998. 32. Neck, V., Kim, J.I.: Radiochim. Acta 89, (2001) 1. 33. Ciaviata, L.: Ann. Chim (Roma) 70, (1980) 551. 34. Ciaviata, L.: Ann. Chim (Roma) 80, (1990) 255. 35. Günther, R., Paulus, W., Kratz, J.V., Seibert, A., Thörle, P., Zauner, S., Brüchle, W., Jäger, E., Pershina, V., Schädel, M., Schausten, B., Schumann, D., Eichler, B., Gäggeler, H.W., Jost, D.T., Türler, A.: Radiochim. Acta 80, (1998) 121.


The Chemistry of Superheavy Elements


Activated complex 100, 101, 112 Activity coefficient 108 Adsorption 105 Atom at a time 96, 102, 103, 106, 108, 109 Canonical 98, 99, 109, 110 Chromatography 106, 107, 108 Collision 100, 112 Coprecipitation 105 Diffusion 100 Distribution coefficient 104, 105, 107 Dynamic partition 103, 106 Edge effects 96, 103, 104, 108, 109 Effects of the media 96, 107, 109 Fluctuation Glückauf Interaction coefficients Isoelectric point 101, 102, 112, 113 107, 114 108 105

Mass action law 96, 97, 98, 99, 100, 102, 109, 110 Maxwell-Boltzmann distribution 101 Mean concentration 98, 99, 100, 109 Microcomponent. 96, 97, 98, 100, 101, 102, 105, 107, 109, 110 Microscopic 96, 97, 111 Partition coefficient 96, 104 104 Partition equilibrium Partition function 97, 98, 109, 110, 111 Potential barrier 112 Probability 97, 98, 99, 100, 102, 104, 106, 110, 111 Sergievskii 108 Single atom 95, 96, 97, 98, 99, 100, 101, 102, 104, 106, 109, 113 SIT 108 Sorption 103, 104, 105 Static partition 104 Stirling 96, 97, 109 Syncristallisation 105 Thermodynamic 95, 96, 97, 98, 101, 102, 103, 107, 108, 109, 112 Transactinide 95, 98, 103 Transport methods 103

Kinetic .95, 96, 97, 100, 101, 102, 103, 109, 113 Macrocomponent 96, 97, 98, 101, 102, 109, 110 Macroscopic 96, 100

Chapter 4 Experimental Techniques
A. Türlera‚ K.E. Gregorichb
a b

Institut für Radiochemie‚ Technische Universität München‚ D-85748 Garching‚ Germany Nuclear Science Division‚ Lawrence Berkeley National Laboratory‚ Berkeley‚ CA 94720



The study of the chemical properties of the heaviest known elements in the Periodic Table is an extremely challenging task and requires the development of unique experimental methods‚ but also the persistence to continuously improve all the techniques and components involved. The difficulties are numerous. First‚ elements at the upper end of the Periodic Table can only be artificially synthesized "one-atom-at-a-time" at heavy ion accelerators‚ requiring highest possible sensitivity. Second‚ due to the relatively short half-lives of all known transactinide nuclides‚ very rapid and at the same time selective and efficient separation procedures have to be developed. Finally‚ sophisticated detection systems are needed which allow the efficient detection of the nuclear decay of the separated species and therefore offer unequivocal proof that the observed decay signature originated indeed form a single atom of a transactinide element. Fast chemical isolation procedures to study the chemical and physical properties of short-lived radioactive nuclides have a long tradition and were applied as early as 1900 by E. Rutherford [1] to determine the half-life of 220 Rn. A rapid development of fast chemical separation techniques [2,3,4,5,6,7, and Ref. 8 for an in-depth review] occurred with the discovery

M. Schädel (ed.)‚ The Chemistry of Superheavy Elements‚ 117-157. © 2003 Kluwer Academic Publishers. Printed in the Netherlands.


The Chemistry of Superheavy Elements

of nuclear fission [9]. Indeed, the discovery of new elements up to Z=101 was accomplished by chemical means [10]. Only from there on physical methods prevailed. Nevertheless, rapid gas phase chemistry played an important role in the claim to discovery of Rf and Db [11]. As of today, the fastest chemical separation systems allow access to the study of nuclides within less than 1 s as demonstrated by the investigation of with a half-life of 0.85 s [12]. Reviews on rapid chemical methods for the identification and study of short-lived nuclides from heavy element synthesis, can be found in [13,14,15,16,17,18,19]. A chemistry experiment with a transactinide element can be divided in four basic steps:
1.) Synthesis of the transactinide element. 2.) Rapid transport of the synthesized nuclide to the chemical apparatus. 3.) Fast chemical isolation of the desired nuclide and preparation of a sample suitable for nuclear spectroscopy. 4.) Detection of the nuclide via its characteristic nuclear decay properties.

Already the synthesis of heavy and superheavy elements is from the technological point of view very demanding. In order to gain access to the longer-lived isotopes of transactinide elements, exotic, highly radioactive target nuclides such as are On bombarded with intense heavy ion beams such as the one hand as intense beams as possible are to be used; on the other hand the destruction of the very valuable and highly radioactive targets has to be avoided. Experimental arrangements that have successfully been used to irradiate exotic targets and to rapidly transport the synthesized transactinide nuclei to a chemistry set-up are discussed in Section 2. The choice of the chemical separation system has to be based on a number of prerequisites that have to be fulfilled simultaneously to reach the required sensitivity: Speed: Due to the short half-lives of even the longest-lived currently known transactinide nuclides‚ see Chapter 1‚ the time required between the production of a nuclide and the start of the measurement is one of the main factors determining the overall yield. In contrast to kinematic separators‚ chemical instrumentation currently allows the investigation of transactinide nuclides with half-lives of a few seconds or longer. The importance of the speed of separation may diminish in

A second group of elements‚ which interfere with the detection of transactinide nuclei‚ are heavy actinides that decay by spontaneous fission (SF). Single atom chemistry: Due to the very low production rates‚ trans­ actinide nuclei must be chemically processed on a “one-atom-at-atime” scale. Guillaumont et al. Experimental Techniques 119 future experiments with the reported longer-lived isotopes of superheavy elements 108‚ 110‚ and 112. Pb‚ Bi‚ and Rn‚ also some At isotopes are of concern. The consequence for single atom chemistry is that the studied atom must be subjected to a repetitive partition experiment to ensure a statistically significant behavior.e. Repetition: Since the moment in time at which a single transactinide atom is synthesized can currently not be determined and chemical procedures often work discontinuously. the chemical separation has to . Rn transfer products. R. These elements are formed in multinucleon transfer reactions with Pb impurities in the target material and/or the target assembly but also with the target material itself. The separation from heavy actinides must be particularly good if SF is the only registered decay mode and if no other information‚ such as the half-life of the nuclide can be derived from the measurement. Some short-lived Po isotopes are observed as daughter nuclides of precursors i. Here a chemical purification of the actinide target materials and a careful selection of the materials used in the target assembly can already reduce the production of unwanted nuclides by orders of magnitude.4.g. Here‚ chromatography experiments are preferred. Nevertheless‚ in order to chemically investigate the recently discovered superheavy elements‚ a kinematic pre-separation might be required to efficiently suppress e. Selectivity: Due to the low production cross sections‚ ranging from the level of a few nanobarns for the production of nuclides of elements Rf and Db‚ down to a level of a few picobarns or even femtobarns for the production of elements with Z > 108‚ the selectivity of the chemical procedure for the specific element must be very high. These are inevitably produced with comparably large cross sections in multinucleon transfer reactions. Two groups of elements are of major concern as contaminants: Due to the fact that many Po isotopes have similar half-lives and/or energies as transactinide elements‚ the separation from these nuclides must be particularly good. [20] have derived an expression equivalent of the law of mass action in which concentrations are replaced by probabilities of finding the species in a given state and a given phase. Thus‚ the classical derivation of the law of mass action is no longer valid‚ see Chapter 3.

have reached the sensitivity to manipulate single atoms or molecules (out of many). The chemical system must be chosen in such a manner that a certain chemical state is probable and stabilized by the chemical environment. the use of position sensitive detectors further enhanced the discrimination against randomly correlated events.120 The Chemistry of Superheavy Elements be repeated with a high repetition rate. The involve the emission of detection of such correlated decay chains requires the event-by-event recording of the data. the detection of the characteristic nuclear decay signature of transactinide nuclei remains currently the only possibility to unambiguously detect the presence of a single atom of a transactinide element after chemical separation. Due to the fact‚ that the studied transactinide elements as well as the interfering contaminants are radioactive and decay with a certain half-life‚ also continuously operating chromatography systems were developed. Also these systems will be included in the current review. This inevitably led to the construction of highly automated chemistry set-ups. Basically‚ four different approaches which involve the direct detection of the nuclear decay of the isolated nuclides have been successful in studying the chemical properties of transactinide elements. Speciation: Due to the fact that transactinide nuclei are detected after chemical separation via their nuclear decay‚ the speciation cannot be determined. Thus‚ thousands of experiments have to be performed. . Thus. Currently‚ the speciation in all transactinide chemistry experiments has to be inferred by carefully studying the behavior of lighter‚ homologue elements. final samples must be suitable for high resolution and SF-spectroscopy (coincident detection of SF fragments). Detection: The unambiguous detection of the separated atom is the most essential part of the whole experiment. In experiments with physical separators. Chemical information can also be obtained by studying the distribution of long-lived grand daughters after completion of the on-line experiment. Two of the systems work in the liquid phase‚ as discussed in Section 3‚ whereas the other two are designed to investigate volatile transactinide compounds in the gas phase‚ as discussed in Section 4. Even though some techniques. Most transactinide nuclei show characteristic decay chains that or the SF of daughter nuclei. such as atomic force microscopy (AFM).

They produce targets of similar quality. target thickness is limiting the compound nucleus recoil ranges because the separation techniques used require the compound nucleus products to recoil out of the target.H. For production of targets from metals and more refractory materials‚ heating can be achieved by electron bombardment. Passage of the beams through the targets produces large amounts of heat.4.F Muggleton [21]‚ although he concentrated on high-temperature vacuum evaporation. Heating can be achieved by passing electric current through a refractory metal boat or using resistance heating on various crucibles. . the recoil ranges are larger.1 Target production techniques Two methods have been used in the fabrication of actinide targets for heavy element studies. The main disadvantage is the relatively low efficiency for collecting the evaporated target material on the target backing foil. A review of many techniques has been published by A.1 ACTINIDE TARGETS To date. the target material must be chemically stable in the highly ionizing environment created by passage of the beam. Evaporation of volatile actinide compounds. With the higher-Z projectiles. In addition. This can be a serious disadvantage with the use of extremely rare and radioactive heavy actinide target materials. For nuclear reactions involving the lighter projectiles. 2. which must be dissipated. These techniques can produce very pure and uniform targets. the highest production rates of isotopes of transactinide elements have been achieved in compound nucleus reactions between light-heavy ion with actinide targets beams Production rates are proportional to both the target thickness and the beam intensity. Targets‚ Recoil Techniques and Gas-jets 121 2. Targets for heavy element chemistry experiments have been produced by the vacuum evaporation of volatile actinide compounds onto stable metallic backing foils. but because of the higher rate of projectile energy loss in the target material and the narrow projectile energy range effective for heavy element production. Experimental Techniques 2. The targets must be physically strong to maintain integrity through handling and irradiation. For vacuum evaporation‚ a relatively volatile compound of the target element is heated to near its vaporization point‚ and the evaporated molecules form a uniform deposit on the nearby cooled target backing foil. the effective target thicknesses are once again limited to The high levels of radioactivity associated with the milligram amounts of these actinide isotopes presents unique challenges for safe handling and irradiation of these targets.1.

Targets up to have been produced by layers. The molecular plating technique can easily be accomplished inside a glove box for containment of the radioactive target material. Extreme care must be taken to produce targets free of impurities. and converting the deposit to the oxide plating successive before plaiting the next layer. Electrospray. The small volumes used facilitate recovery of actinide materials. Nitrate or chloride compounds of the actinide element are suspended in a small volume of organic solution (usually isopropanol or acetone).H. An extremely fine glass capillary is drawn and an electrode is inserted into the capillary. Muggleton [21] and references therein‚ an actinide compound is dissolved in a non­ conducting organic solvent. A typical plating cell is shown in Figure 1. Once a high voltage is .F. Electrodeposition or molecular plating has been the method of choice for production of the small-area actinide targets for use in production of heavy element isotopes for chemical studies. Sub-milligram quantities of actinide elements have been used and the deposition yield can approach 100%. and a high voltage is applied between the solution and the target backing foil.122 The Chemistry of Superheavy Elements Molecular plating. The capillary is filled with the solvent containing the actinide compound‚ and the capillary tip is placed within a few centimeters of the target backing foil. With the electrospray‚ see the review by A. form by heating to Such techniques have been described by several authors [22‚23‚24‚25].

Yakushev [28] has overcome the small target area limitation by placing a supporting grid over a large-area target and using an electrostatic beam wobbler to spread the beam out over a much larger area. While large area and thick targets have been produced by this technique. target areas have been limited to Heating of the target by passage of the beam is inversely proportional to the cross sectional area of the beam. Experimental Techniques 123 applied between the electrode and the metal target backing foil. In the double window system. These thick foils Be or are especially attractive when considering the mechanical stability of extremely radioactive actinide targets. These devices are similar to those used in ink-jet printers. 2. highly efficient target cooling is necessary. Since both the vacuum isolation foil and the target backing foil must hold a pressure difference of greater than 1 bar. an increase in the target size (or area) would allow the use of higher beam intensities. Double-window systems and forced gas cooling. Variations on the double-window target system have traditionally been used for heavy element production with actinide target materials. Piezoelectric pulsed drop jet devices have been used for target production [26]. Because of the mechanical stresses associated with the pressure differences across the foils. While some . Cooling gas at pressures near 1 bar is forced at high velocity through a narrow gap between the vacuum isolation foil and the target backing foil. such as HAVAR.4. relatively thick metal foils.1. a fine spray is emitted from the capillary which immediately dries on the backing foil. To allow the highest beam intensities. resulting in deposition of heat in the target. cooling both foils. The heat generated must be removed to prevent damage to the target. Ink-jet techniques. Clearly.2 Target cooling The projectile beam loses energy upon passing through the target backing and the target. the spraying of aerosol-sized particles of an extremely radioactive solution poses challenging safety problems. with actinide target materials. have been used. a vacuum isolation foil is placed just upstream of the target backing foil (with the target material on the downstream side of the backing foil). This technique has essentially been supplanted by the molecular plating process. A. The double-window target system has been developed [27] for use with targets on relatively thick backing foils.

2. This rotating target has allowed the use of modern high-intensity accelerated beams for heavy element chemistry experiments [30].1.M.124 The Chemistry of Superheavy Elements fraction of the beam is lost on this grid‚ much larger beam intensities‚ and therefore higher production rates were achieved. A picture of this rotating target after irradiation with of a beam (a factor of four larger than possible with a up to fixed target) is presented in Figure 3. Each of the targets would be irradiated at approximately an 11% duty factor. Thus‚ as illustrated in Figure 2‚ it should be possible to use electrostatic deflection plates together with pulsed highvoltage supplies to deliver the beam alternately among an array of several targets. In this way‚ an effectively larger area target could be used without the beam loss and heating associated with a target grid. Nitschke has shown that when using a pulsed beam (with beam pulse widths on the order of 10 ms)‚ even though the instantaneous beam intensity on the target is higher‚ similar average beam intensities can be used without damage to the target [27]. A rotating been used in heavy element chemistry experiments at the Gesellschaft fur Schwerionenforschung (GSI) [29]. . J.3 Rotating targets Another method for effectively spreading the beam heating over a larger target has recently target area is the use of rotating targets. In Figure 2‚ a high intensity beam is distributed among a square array of nine targets on a 5-ms timescale.

Obvious limitations arise with the use of highly radioactive heavy actinide targets in the search for shortlived heavy element isotopes.4. At the end of an irradiation‚ the long-lived radionuclides could be chemically separated from the target. 2.2 RECOIL TECHNIQUES In the early days of accelerator-based radiochemical separations‚ thick targets were irradiated‚ allowing the compound nucleus products to stop in the target material. Experimental Techniques 125 2.1 Recoil catcher foils When a compound nucleus is formed in the reaction of a projectile beam with a target nucleus‚ the compound nucleus is formed with the momentum of the beam particle. Perhaps the first use of the recoil catcher technique for heavy element studies was with the chemical separations used in the 1955 discovery of Mendelevium [31]. These recoiling reaction products can be stopped in a metal foil placed directly downstream of the target.2. By using this recoil catcher method [10]‚ chemical separation of the heaviest elements is facilitated because only a small fraction of the radioactive target material is transferred to the recoil catcher foil‚ and the recoil catcher foil material can be chosen to facilitate its dissolution and chemical removal. If the target layer is thin enough‚ this recoil momentum is sufficient to eject the compound nucleus product from the target. With the recoil catcher foil technique‚ the time required for removal of the foil‚ and dissolution and .

2 Aerosol gas-jets To achieve faster chemical separation times‚ the aerosol gas-jet transport technique has been used to deliver transactinide isotopes form the target chamber to various chemical separation devices. After stopping in the gas‚ the reaction products become attached to the aerosol particles. . Widely used were KCl aerosols which can easily be generated by sublimation of KCl from a porcelain boat within a tube furnace. Products of nuclear reactions are allowed to recoil out of a thin target‚ and are stopped in a gas at a pressure usually above 1 bar. Transport times on the order of one second have been achieved.126 The Chemistry of Superheavy Elements separation of the foil material results in chemical separation times longer than a few minutes. The collected aerosol particles‚ containing the nuclear reaction products‚ can be made rapidly available for chemical separation. At the downstream end of the capillary‚ the He goes through a supersonic expansion into the vacuum‚ exiting in a broad cone. The principles behind the aerosol gas-jet transport technique have been presented by H. Carbon aerosol particles of similar dimensions were generated by spark discharge between two carbon electrodes. Wollnik [32]. 2. Many aerosol materials have been used‚ and the aerosol material can be specifically chosen to minimize interference with the chemical separation being conducted. The gas is usually helium because of the relatively long recoil ranges. The same concentrations of few times technique could be applied to produce aerosols. Since the half-lives of transactinide isotopes are on the order of one minute or less‚ this technique has not been used for transactinide chemistry experiments. By choosing a temperature between 650°C and 670°C‚ specially tailored aerosols with a mean mobility diameter of about 100 nm and number could be generated. The large transport efficiencies through the capillary for the aerosol gas-jet technique can be explained in terms of the laminar flow profile of the gas inside the capillary [32]. Transport efficiencies of over 50% have routinely been achieved for transport capillary lengths over 20 meters. The He gas is seeded with aerosol particles.2. According to Bernoulli's law‚ the gas pressure at the center of the capillary‚ where the velocity is highest‚ is lower than near the capillary walls. Thus‚ when the sub aerosol particles drift away from the center of the capillary‚ they are subject to a restoring force toward the center of the capillary. The aerosol particles‚ having much lower random thermal velocities are ejected from the tip of the capillary in a narrow cone‚ and can be collected on a foil or filter. The gas and activity-laden aerosol particles are sucked through a capillary tube to a remote site‚ by applying vacuum to the downstream end of the capillary.

A schematic of the experiment is presented in Figure 4. These proof-of-principle experiments showed the practicality of a physical pre-separation of transactinide nuclides before chemical separation.3 Kinematic separators and gas-jets Atoms of the transactinide elements are produced at extremely low rates: atoms per minute for Rf and Db‚ down to atoms per day for elements 106­ 108.0-s was produced in the reaction‚ and separated from all other reaction products with the Berkeley Gas-filled Separator [35]. The He gas in the RTC was seeded with KC1 aerosol particles‚ and the atoms became attached to the aerosols‚ and were transported through a 20-m capillary to the SISAK chemical separation system‚ where the chemical separation and detection were performed. For these experiments‚ 4. Thus‚ it has been proposed that a kinematic separator could be coupled to a transactinide chemistry system with an aerosol gas-jet device‚ and a workshop has been held to discuss the merits and design of such a device [33]. They are produced among much larger amounts of “background” activities which hinder the detection and identification of decay of the transactinide atoms of interest. Coupling of the Berkeley Gas-Filled Separator (BGS) with a transactinide chemical separation system has been accomplished at the Lawrence Berkeley National Laboratory in some proof-of-principle experiments [34].2. .4. In the focal plane area of the BGS‚ the MYLAR foil and were stopped in a volume of recoils passed through a He at a pressure of 2 bar in the Recoil Transfer Chamber (RTC) [36]. Experimental Techniques 127 2. For these reasons‚ there is a recognized need for a physical pre-separation of the transactinide element atoms before chemical separation.

Liquid-phase chemical separation techniques have been used for over 100 years‚ thus their utility for separation and isolation of the chemical elements has been demonstrated. The time from end of collection of aerosols to the beginning of counting of the transactinide chemical fractions was as short as 50 seconds‚ and the collection-separationcounting cycle could be repeated every 60-90 seconds. These include: a) a special collection turntable for easy collection of the gas-jet samples which also signaled the data acquisition computer at the start and end of collection for each sample. For the Rf the 8. Today‚ most of the research has turned to automated chemical separation techniques.29-MeV chemistry‚ 78-second reaction. 3.1 Manual liquid-liquid extractions Manually performed liquid-liquid extractions have been used for the study of chemical properties of Rf [37‚38‚39‚40] and Db [41] in Berkeley. 3.128 The Chemistry of Superheavy Elements Techniques and Instruments for Liquid-Phase Chemistry 3. To minimize the separation and sample preparation time‚ phase volumes were For these experiments‚ several specially developed kept to techniques and apparatus were necessary.1 MANUAL LIQUID-PHASE CHEMICAL SEPARATIONS The early chemical separations with the heaviest elements were performed manually. These adaptations have been developed to overcome the single-atom and short half-life limitations inherent in the study of transactinide element chemical properties.22-8.1. Identification of particles from the decay of was produced by the was made by measuring and/or the 8. b) small syringes with hand-made transfer pipettes for rapid pipetting of volumes as small as c) the ultrasonic mixer‚ which was made by modification of a commercially available home ultrasonic humidifier. e) techniques for rapidly and reliably drying the organic phase at the center of an Al disc or glass plate. The microscale liquid-liquid extraction technique used in these studies was based on techniques developed for the study of Lr chemical properties [42‚43]. and f) a set of detection chambers which could be quickly loaded‚ evacuated‚ and which signaled the acquisition computer as to the start and stop of the measurement for each sample. d) a specially modified centrifuge which reached full speed and returned to a full stop in a few seconds and also signaled the data acquisition computer to record the chemical separation time. Adaptations of these well-understood separation techniques have been applied to the transactinide elements.32 MeV .

Additionally‚ extraction systems which come to equilibrium in the 5-10 second phase contact time must be chosen. By comparing the Rf or Db detection rate under a certain set of chemical conditions to the rate observed under chemical control conditions known to give near 100% yield‚ distribution coefficients between about 0.45-MeV particles from the decay of and/or the 8.2 and 5 can be determined. Detection rates for the were as parent and the high as 5 events per hour of experiments. in 1970. For this reason‚ measurement of distribution coefficients is somewhat difficult. Although manually performed column chromatography separations were further use of column used [43] for studies with 3-minute .2 Manual column chromatography The first liquid-phase transactinide chemical separations were manually performed Rf cation exchange separations [42] using as eluent‚ performed by R.9-second daughter. were approximately one event per hour of Detection rates for the experiments.65 MeV particles for the decay of the 3. If the control experiments are performed nearly concurrently‚ many systematic errors‚ such as gas-jet efficiency and experimenter technique‚ are cancelled out.J. Identification of was made by measuring the 8. The detection was made more certain by detecting correlated pairs of decays from both the daughter.59-8. These experiments showed that Rf had a charge state of 4+ (or higher) and that its chemical properties are distinctly different from those of the actinides. The were collected products from the nuclear reaction‚ along with the and run through a small cation from the Pt disk in a small volume of exchange resin column. Experimental Techniques 129 particles for the decay of the 26-second daughter.4. Silva et al. Because of interference from the radioactive decay of other nuclides (which are typically formed with much higher yields)‚ extraction systems with relatively high decontamination factors from actinides‚ Bi‚ and Po must be chosen‚ and the transactinide activity can only be measured in the selectively extracting organic phase. 3. The detection was made more certain by detecting correlated pairs of decays from both the parent and the daughter. For the Db chemistry‚ 34-second was produced by the reaction.1. Under these conditions‚ all cations with charge and eluted from the states of 4+ or higher were complexed with the column. The newly discovered 78-second was produced in the reaction‚ Pt foils which were transported to the recoils were stopped on and other the chemical separation area with a rabbit system.

1.2. 3.2 AUTOMATED LIQUID-PHASE CHEMICAL SEPARATIONS As chemical investigations progress from Z= 104-105 (with detection rates of atoms per hour)‚ through Z= 106-108 (with detection rates of atoms per week)‚ and on to even heavier elements (with expected detection rates of only a few atoms per month)‚ manually performed chemical separations become impractical.3 Future techniques for manual liquid-phase separations Manually performed liquid-phase chemical separations will continue to be used‚ especially for investigations of Rf and Db‚ with their relatively large production rates. 3. By picking up the gas-jet sample in a small volume of an appropriate aqueous phase‚ and pulling it through the chemically selective packing inside the syringe body‚ and then forcing it back through the packing on to the sample preparation disk‚ a very fast and simple equivalent of a column separation could be performed. 3. [15‚ 44‚ 45]. With the advent of the use of kinematic pre-separators‚ as described in Section 2. It is no longer necessary to have the highest separation factors from interfering Bi‚ Po‚ and actinide radioactivities‚ so simpler separations which are more specific to the transactinide element being studied can be used. With the automated liquid-phase chemical separation systems that have been developed to date‚ faster chemical separation and sample preparation times have been achieved.1 Automated Rapid Chemistry Apparatus (ARCA) Extensive studies of chemical properties of transactinide elements‚ Rf‚ Db‚ and Sg have been performed with the Automated Rapid Chemistry Apparatus (ARCA)‚ see summaries in Ref. In addition‚ the precision and reproducibility of the chemical separations has been improved over that obtainable via manually performed separations. New devices and techniques will be developed to minimize the separation and sample preparation time and to minimize the repetitive labor required.2 above‚ the requirements of the chemical separation have been relaxed. To improve the speed and reduce cross contamination‚ the ARCA II was built‚ featuring two magazines of 20 miniaturized ion exchange columns [46]. By miniaturizing the columns‚ the elution .130 The Chemistry of Superheavy Elements chromatography for studying the chemical properties of the transactinides awaited the development of the automated techniques described below. With the large number of columns‚ cross contamination between samples can be prevented by using each column only once. These relaxed separation requirements will allow development of simpler chemical separation techniques‚ and may lead to a new interest in manually performed chemical separations.2. One idea being explored is the use of extraction chromatography packings inside small syringes.

A photograph and a schematic of the ARCA microprocessor-controlled column chromatography system are presented in Figure 5. A slider below the ion exchange column is moved at the appropriate time to collect the chemical fraction of interest on a hot Ta disk. At the end of a suitable collection time‚ the slider is moved to position the collection site above one of the miniature ion exchange columns. A suitable aqueous solution is used to dissolve the aerosols and load the activities onto the ion exchange material in the column below.4. The two magazines of chromatography columns (CL and CR in the schematic) can be moved independently. A sample pulse-height analysis is prepared by rapid evaporation suitable for of the chemical fraction on the Ta disk‚ which is heated from below by a hot­ plate‚ and from above by a flow of hot He gas and a high-intensity lamp. Selective elutions of transactinide elements are carried out by directing appropriate solutions through the column. During a chemical separation on CL‚ the right column‚ CR‚ is prepared by flowing an appropriate solution through it. Experimental Techniques 131 volumes‚ and therefore‚ the time needed to dry the final sample to produce a source for spectroscopy‚ is much reduced. The final samples are then manually placed in a detector chamber for pulse-height spectroscopy. With ARCA II‚ activity-bearing aerosols are collected from a gas-jet in a small spot on a slider (seen at the center of the schematic). After the separation on CL‚ the magazine is moved forward‚ placing a new column in the CL position‚ the next .

3. In this way‚ up to 40 separations can be carried out‚ at time intervals of less than one minute‚ with each separation performed on a freshly prepared‚ unused column. The three-column . chambers containing large-area PIPS This robotic sample preparation and counting technology‚ together with mechanical improvements in the chemical separation system‚ has resulted in an automated column chromatography system that can run almost autonomously‚ whereas several people were required to operate the ARCA II system for a transactinide chemistry experiment. 3. Transactinide chemistry experiments with Rf have been carried out with the AIDA apparatus [59]. Since the transactinide isotopes typically decay by emission to relatively long-lived actinides‚ a technique has been developed to perform continuous chemical separations on the transactinide element decay of the isotopes‚ and detect their presence by observing the long-lived daughters.2. More details and results are discussed in Chapter 5. Since the daughter activities are typically produced via multinucleon transfer reactions at rates much greater than the transactinide element production rates‚ special techniques must be used.132 The Chemistry of Superheavy Elements separation is performed on CR while CL is being prepared for the subsequent separation.3 Continuous on-line chromatography – identifying the heavy element daughters One of the difficulties in studying the chemical properties of the transactinide elements is presented by their relatively short half-lives. The time and labor required for performing batch-wise experiments and preparing samples suitable for pulse-height spectroscopy presents a daunting task. Transactinde chemical separations with ARCA II have been performed with Rf [47‚48]‚ Db [49‚50‚51‚52‚53]‚ and Sg [54‚55]. While the apparatus for collection of aerosols‚ and performing multiple chemical separations on magazines of miniaturized ion exchange columns is very similar to that in ARCA II‚ AIDA has automated the tasks of sample preparation and placing the samples in the detector chambers.2 Automated Ion-exchange Separation Apparatus coupled with the Detection System for Alpha Spectroscopy (AIDA) Building upon the design of ARCA II an automated column separation apparatus‚ AIDA [56‚57‚58] has recently been built. Using robotic technology‚ the selected fractions are dried on metal planchettes‚ and are then placed in vacuum detectors.2.

On the other hand. allowing the Db atoms to pass through to the second column. The third column quantitatively retains the longer-lived daughter activities. In the three column technique.63].65]. 3. the retention time on the second column (and thus the distribution coefficient) of the nuclide of interest is can be measured by comparing the relative amounts of the longlived daughter activity on the third column and in the effluent of the third column. and Fm activities were retained on the first column. and assayed for the of the great-granddaughter of The separation technique used for the Db study was adapted from the slightly more complicated technique developed by G. Experimental Techniques 133 technique has been developed and applied to the study of the solution chemistry of Rf by Z. the first column is used to remove all of the daughter activities initially present. the daughter activities are chemically separated from this third column. At the end of a suitable production and chemical separation cycle. 34-s was produced in the reaction and transported to the chemical separation apparatus with an aerosol gas-jet. Szeglowski et al.2. [62. the daughter is strongly adsorbed on the third. Md. Activities are delivered to the apparatus with an aerosol . this third column should contain only Lr. Trubert et al. and Fm (via they are desorbed from the second column and pass to the third column. Three-column systems have been developed in hopes of performing chemical studies with other transactinides [64. retained. the daughter atom will be found in the effluent from the third column. The chemical conditions are chosen so that the retention time for the nuclide of interest is on the order of its half-life on the second column. As the Db atoms decay to Lr. In this more general version. The first column was used to separate all of the directly-produced daughter activities. for the study of chemical properties of Db [61]. Md. Since all directly-produced Lr. once again. as used by D.4. see also Chapter 5. The activities delivered by the gas-jet were continuously dissolved in an appropriate aqueous solution and passed through a series of three ion exchange columns. Pfrepper et al. If the parent nuclide decays while on the second column. and very short on the third column. and Fm atoms that are the decay descendents of Db atoms which were retained on the second column. In this way. [60].4 SISAK The SISAK (Short-lived Isotopes Studied by the AKUFVE-technique‚ where AKUFVE is s Swedish acronym for an arrangement of continuous investigations of distribution ratios in liquid extraction) system performs continuous liquid-liquid extractions using small-volume separator centrifuges [66]. where they are quantitatively and EC-decay). if the parent atom survives passage through the second column (and the third). Md.

This modular separation and detection system allows the use of wellunderstood liquid-liquid extraction separations on timescales of a few seconds‚ with detection efficiencies near 100%.134 The Chemistry of Superheavy Elements gas-jet. A schematic of the BGSchemical separation and detection of 4-s RTC-SISAK apparatus is presented in Figure 6.3‚ pre-separation with the Berkeley Gas-filled Separator before transport to and separation with SISAK allowed the [34]. The aqueous solution is then mixed with an organic solution and the two liquid phases are separated in a separator centrifuge. This extremely fast chemical separation and detection system has been used with a sub-second nuclide [67‚68]. . A scintillation cocktail is then mixed with the organic solution‚ and this is passed through a detector system to perform liquid scintillation alpha pulse-height spectroscopy on the flowing solution. These proof-of-principle experiments have paved the way for detailed liquid-liquid extraction experiments on short-lived transactinide element isotopes.2. However‚ for the transactinide elements‚ which are produced in much lower yields with larger amounts of interfering of the transactinide isotopes failed. As activities‚ detection of the described in Section 2. The gas-jet is mixed with the aqueous solution to dissolve the activity-bearing aerosols‚ and the carrier gas is removed in a degasser centrifuge.

Gäggeler and co-workers was then successful in studying volatile transactinide compounds from Rf up to Bh [76‚77‚78‚79]‚ see Chapter 7 for a detailed discussion. The technique was pioneered by I. 4. A number of prerequisites that need to be fulfilled simultaneously to accomplish a successful chemical experiment with a transactinide element are almost ideally met by gas chromatography of volatile inorganic compounds. For isotopes of these superheavy elements‚ production rates are as low as a few atoms per month‚ making any chemical separations with these elements especially difficult. New highly efficient aqueous-phase chemical separation systems will have to be developed. Zvara and co-workers at the Dubna laboratory and involved first chemical studies of volatile Rf‚ Db and Sg halides and/or oxyhalides [73‚74‚75]. Gas phase separation procedures are fast‚ efficient and can be performed continuously‚ which is highly desirable in order to achieve high overall yields.2. Experimental Techniques 135 3. The experimental set-ups and the techniques involved are presented in Section 4.W. In all these . Finally‚ nearly weightless samples can be and SF-spectroscopy of prepared on thin foils‚ which allow the separated products with good energy resolution and in high‚ nearly detection geometry. see Chapter 7 for a detailed discussion.5 Future techniques for automated liquid-phase chemical separations Experiments have been carried out to measure the chemical properties of elements through Hs‚ element 108.4. Recent experiments have resulted in claims of isotopes of elements 112 and 114 with half-lives of at least a few seconds [69‚70‚71‚72]: long enough for future chemical studies. Since these separations will be operating for months at a time‚ they must be designed to run autonomously‚ presenting unique new challenges to the aqueous-phase chemists. Techniques and Instruments for Gas-Phase Chemistry Despite the fact that only few inorganic compounds of the transition elements exist‚ that are appreciably volatile below an experimentally still easily manageable temperature of about 1000°C‚ gas-phase chemical separations played and still play an important role in chemical investigations of transactinide elements. Early on‚ gas-phase chemical separations played an important role in the investigation of the chemical properties of transactinide elements. Since the synthesis of transactinide nuclei usually implies a thermalization of the reaction products in a gas volume‚ a recoil chamber can be connected with a capillary directly to a gas chromatographic system. A new technique‚ named OLGA (On-line Gas chromatography measurement of final Apparatus)‚ which allowed the products‚ developed by H.2.

1.1 Thermochromatography In thermochromatography‚ see e. Reference 14 for a review‚ a carrier gas is flowing through a chromatography column‚ to which a negative longitudinal temperature gradient has been applied.4.1 THERMOCHRMOMATOGRAPHY AND ISOTHERMAL CHROMATOGRAPHY For the experimental investigation of volatile transactinide compounds two different types of chromatographic separations have been developed‚ thermochromatography and isothermal chromatography. Only recently‚ the technique of synthesizing volatile species in-situ in the recoil chamber combined with a new cryo thermochromatography detector [80] was successful in the first chemical identification of Hs (element 108) [30] and appears to be a valid concept for first chemical investigations of element 112 in the elemental state‚ see Section 4. 4. Open or filled columns can be employed. 4.3. The basic principles of thermochromatography and isothermal chromatography are explained in Figure 7. Sometimes also combinations of the two have been applied.g. Species‚ that are volatile at the starting point‚ are transported .136 The Chemistry of Superheavy Elements experiments‚ the isolated transactinide nuclides were unambiguously identified by registering their characteristic nuclear decay‚ see Section 4.

2 Isothermal chromatography In isothermal chromatography‚ a carrier gas is flowing through a chromatography column of constant‚ isothermal temperature. Thus‚ the emitted radiation can easily be detected by scanning the length of the column with a detector. This retention time can be determined either by injecting a short pulse of the species into the carrier gas . The two variants (continuous or discontinuous) result in slightly different peak shapes.and long-lived nuclides can be registered throughout the duration of the experiment. After completion of the experiment‚ the track detectors are removed and etched to reveal the latent SF tracks. Thermochromatographic separations are the method of choice to investigate species containing long-lived nuclides that decay either by ECdecay‚ or by the emission of highly energetic particles or [85‚86‚87‚88‚89‚90‚91‚92]. Due to the decreasing temperature in the column‚ the time the species spend in the adsorbed state increases exponentially.4. 4. Different species form distinct deposition peaks‚ depending on their adsorption enthalpy on the column surface and are thus separated from each other. Thus‚ the position of each decay in the column contributes chemical information about of the investigated species. A characteristic quantity is the deposition which depends on various experimental parameters‚ see temperature Chapter 6. However‚ the temperature range for which SF track detectors can be applied is limited‚ due to the annealing of tracks with time. By inserting SF track detectors into the column‚ SF decays of short. Experimental Techniques 137 downstream of the column by the carrier gas flow. The chromatographic resolution is somewhat worse for the continuous variant.1. Depending on the temperature and on of the species on the column surface‚ the species travel slower through the length of the column than the carrier gas. The mixture of species to be separated can be injected continuously into the column [81‚82‚83‚84]‚ or the experiment can be performed discontinuously by inserting the mixture of species through the hot end of the chromatography column‚ and removing the column through the cold end after completion of the separation. Open or filled columns can be employed. It should also be noted‚ that in thermochromatography all information about the half-life of the deposited nuclide is lost‚ which is a serious disadvantage‚ since SF is a non-specific decay mode of many actinide and transactinide nuclides. However‚ thermochromatography experiments with transactinides decaying by SF have an unsurpassed sensitivity (provided that the chromatographic separation from actinides is sufficient)‚ since all species are eventually adsorbed in the column and the decay of each nuclide is registered. The detection of nuclides decaying by emission or SF decay is more complicated. Columns made from fused silica have also been used as SF track detectors [75].

The temperature depends on various experimental parameters (see Chapter 6). 4. In order to determine the temperature‚ a measurement sufficiently above and below this temperature is required. The half-life of the nuclide is thus used as an internal clock of the system. The yield of the species at the exit of the column changes within a short interval of isothermal temperatures from zero to maximum yield. A disadvantage of isothermal chromatography concerns the determination of on the column surface of transactinide nuclei.2 INSTRUMENTATION FOR EARLY GAS-PHASE CHEMISTRY EXPERIMENTS WITH TRANSACTINIDE ELEMENTS A schematic drawing of the chemical apparatus constructed for the first chemical isolation of element 104 in Dubna is shown in Figure 8 [104]. Furthermore‚ it must be demonstrated that the experiment was performing as expected and the nonobservation of transactinide nuclei was not due to a malfunctioning of the apparatus. A characteristic quantity is the temperature at In this which half of the introduced nuclides are detected at the exit case‚ the retention time in the column is equal to the half-life of the introduced nuclide. It can be shown‚ that for similar gas flow rates and column dimensions By varying the isothermal temperature‚ an integral chromatogram is obtained. Since volatile species rapidly emerge at the exit of the column‚ they can be condensed and assayed with nuclear spectroscopic methods.138 The Chemistry of Superheavy Elements and measuring the time at which it emerges through the exit of the column [93‚94]‚ or by continuously introducing a short-lived nuclide into the column and detecting the fraction of nuclides that have decayed at the exit of the column [95‚96‚97‚98‚99]. The yield of different species at the exit is measured as a function of the continuously‚ but isothermally‚ increasing temperature [93‚100‚101‚102‚103]. Less volatile species are retained much longer and the radionuclides eventually decay inside the column. Such an approach is very beam time consuming. A variant of isothermal chromatography using long-lived radionuclides is temperature programmed chromatography. On-line isothermal chromatography is ideally suited to rapidly and continuously separate short-lived radionuclides in the form of volatile species from less volatile ones. . Since for transactinide elements this temperature is a priori unknown‚ several measurements at different isothermal temperatures must be performed‚ which means that long measurements are required below temperature that demonstrate that the transactinide compound is the retained long enough that most of the nuclei decayed in the column.

5 mm diameter were drilled. An Al foil of 9 thickness served as vacuum window. Both sides of the target were flushed with nitrogen at 250°C or 300°C. In section I‚ a target was bombarded at the inner beam of the U-300 cyclotron at Dubna with ions.4. Experimental Techniques 139 A diagram showing different sections of the apparatus is displayed in Figure 9. The whole target block was heated . The with a thickness of about 800 thickness. In the outer housing of the target chamber‚ a number of closely spaced holes of 1. The was deposited as oxide on aluminum foil of 6-9 target was held between two plates made of an aluminum alloy‚ into which a number of closely spaced holes of 1.5 mm were drilled‚ which matched the holes of the target holder.

140 The Chemistry of Superheavy Elements with a heater. The filter in section VI served for the chemisorption of Hf nuclides in ancillary work with long-lived nuclides. Aerosols were apparently formed by the interaction of the chloride vapors with oxygen present in the nitrogen carrier gas. Further experiments with a slightly modified apparatus [106] were conducted immediately after the experiments described here. It was found that carriers with a vapor pressure similar to that of the investigated compound yielded optimum transfer efficiencies [81]. The space behind the target was limited with an Al foil and was about 11 mm deep and had a volume of about Reaction products recoiling from the target were thermalized in a rapidly flowing stream of (18 1/min) and were transferred to section II. This filter was intended to trap large aggregate particles [105]. This section consisted of an outer steel column into which tubular inserts of various materials glass) could be inserted [104]. which was consisted of a 4 m long column with an inner diameter of 3. which recorded SF fragments of the SF decay of a Rf nuclide. The addition of carriers was essential since in this manner the most reactive adsorption sites could be passivated. that had previously been synthesized and identified by a team of physicists at Dubna.5 mm. Zvara and co-workers identified multiple SF tracks in the mica detectors when they used glass surfaces and temperatures of 300°C [104]. etched and analyzed for latent fission tracks. that the experimental set-up was suited to study the short-lived Rf isotope [81]. The whole apparatus was built to chemically identify an isotope of Rf decaying by SF with a half-life of 0. Section IV contained a filter. I. Volatile reaction products were flushed into the chromatographic section (section III). Volatile products passing the filter in section IV now entered the detector in section V. where the chlorination of the reaction products took place. In section VII the chloride carriers were condensed. . They had shown in preparatory experiments with Hf. and thus. In a number of experiments. A number of possible sources of SF tracks in the mica detectors other than the SF decay of an Rf isotope were discussed and ruled out. as a rule. This filter had a stainless steel jacket into which. A total of 63 SF events were attributed to the decay of an Rf nuclide. The transfer efficiency was measured to be > 75% and the transfer time was only about In the and were continuously reaction chamber of section II. crushed column material from section III was filled [104]. The mica plates were removed after completion of the experiment. that indeed the transfer of Hf through the apparatus occurred within less than 0.3 s. vapors of added as chlorinating agents and as carriers [104].3 seconds. This detector consisted of a narrow channel of mica plates.

4.4. A first version of OLGA (I) was developed and built by H.3 ON-LINE GAS-PHASE CHEMISTRY WITH DIRECT IDENTIFICATION OF TRANSACTINIDE NUCLEI One of the most successful approaches to the study of volatile transactinide compounds is the so-called OLGA (On-Line Gas chromatography Apparatus) technique. Experimental Techniques 141 Similar thermochromatography set-ups‚ always relying on the registration of SF tracks‚ were employed by I.W. However‚ due to the fact that in all these experiments the separated nuclides were identified by the non-characteristic SF decay‚ and no further information such as the half-life of the investigated nuclide could be measured‚ most of the experiments fell short of fully convincing the scientific community‚ that indeed a transactinide element was chemically isolated [11‚112‚113]. Nevertheless‚ the ideas conceived at Dubna and the techniques invented to chemically study short-lived single atoms‚ paved the way to gas chromatography experiments that allowed the unambiguous identification of the separated transactinide nuclei. Volatile elements were separated in a stream of He and 25 s hydrogen gas at 1000°C from non volatile actinides and other elements. Contrary to the technique in Dubna‚ reaction products are rapidly transported through a thin capillary to the chromatography setup with the aid of an aerosol gas-jet transport system‚ see Subsection 2.D. Reactive gases are introduced to form volatile species‚ which are transported downstream by the carrier gas flow to an adjoining isothermal section of the column‚ where the chromatographic separation takes place. With typical He flow rates of 1 to 2 1/min and inner diameters of the capillaries of 1. von Dincklage and co-workers [96]. Gäggeler and co-workers for the search of volatile superheavy elements‚ and tested with [114].2. At the exit of the column‚ the separated nuclei were condensed on thin metal foils mounted on a rotating wheel (ROtating Wheel Multidetector Apparatus‚ ROMA [115‚116]) and periodically moved in front of solid state detectors‚ and SF events were registered in an event-by-event mode.2.5 to 2 mm‚ transport times of less than 10 s were easily achieved. volatile emitting Hf While the gas chemical isolation of short-lived . where A first attempt to identify the nuclide after chemical isolation as is described by R. Zvara and co-workers to chemically identify the next heavier transactinide elements Db [13‚74‚107]‚ and Sg [75‚108‚109‚110]‚ whereas experiments to chemically identify Bh [111] yielded negative results. The aerosols carrying the reaction products are collected on quartz wool inside a reaction oven. This way‚ the chromatography system and also the detection equipment could be set up in an accessible‚ fully equipped chemistry laboratory close to the shielded irradiation vault.


The Chemistry of Superheavy Elements

nuclides was successful‚ the experiment with Rf failed‚ since the employed surface barrier detectors were destroyed by the prolonged exposure to the chlorinating agent. The first successful gas chemical studies of volatile halides of Rf [76] involving the unambiguous detection of time correlated nuclear decay chains was accomplished with OLGA(II) [98]. Instead of condensing the separated molecules on metal foils after passing the chromatography column‚ they were attached to new aerosol particles and transported through a thin capillary to the detection system. This so-called reclustering process was very effective and allowed to collect the aerosols on thin polypropylene foils in the counting system (ROMA or MG‚ Merry Go round [117]). Thus‚ samples could be assayed from both geometry‚ which doubled the counting efficiency. A crucial sides in a detail was the use of then newly available PIPS (passivated ion-implanted planar silicon) detectors (instead of surface barrier detectors) which were resistant to the harsh chemical environment. At the same time the Paul Scherrer Institute (PSI) tape system was developed [98]‚ which allowed to significantly reducing the background of long-lived SF activities that counting geometry accumulated on the wheel systems. However‚ only a could be realized. An improved version of OLGA(II) was built at Berkeley and was named Heavy Element Volatility Instrument (HEVI) [99]. With both instruments the time needed for separation and transport to detection was about 20 s‚ the time consuming process being the reclustering. In order to improve the chromatographic resolution and increase the speed of separation‚ OLGA(III) was developed [17]. Using a commercial gas chromatography oven and a 2 m long quartz column which ended in a much smaller‚ redesigned recluster unit‚ the overall separation time could be reduced by one order of magnitude‚ while the chromatographic resolution was much better. A schematic of OLGA(III) connected to either a rotating wheel or a tape detection system is shown in Figure 10. OLGA(III) has very successfully been applied to study volatile halides and/or oxyhalides of Rf [118]‚ Db [119]‚ Sg [78‚120] and Bh [121]‚ see Chapter 7 for a detailed discussion. In all these experiments the separated transactinide nuclides were unambiguously identified via their nuclear decay properties. An improved version of OLGA(I)‚ named HIgh-Temperature on­ line Gas chromatography ApparatuS (HITGAS)‚ has been developed at Forschungszentrum Rossendorf and successfully applied to study oxide hydroxides of group 6 elements including Sg [122‚123].

4. Experimental Techniques


In order to further reduce the background of unwanted nuclides‚ the so-called parent-daughter recoil counting modus was implemented at the rotating wheel systems. Since the investigated transactinide nuclei decay with a characteristic decay sequence involving the decay and/or SF decay of daughter nuclei‚ the significance of the observed decay sequence can be enhanced by observing the daughter decays in a nearly background free counting regime. This can be accomplished in the following manner‚ see example with in Figure 11. In the parent mode‚ a atom is deposited on the top of a thin foil together with a sample of the aerosol transport material. The wheel is double-stepped at preset time intervals to position the collected samples successively between pairs of detectors. When the is detected in the bottom of a detector pair‚ it is assumed that the daughter has recoiled into the face of the top detector. The wheel is single-stepped to remove the sources from and daughters is between the detector pairs‚ and a search for the made for a second preset time interval‚ before single-stepping the wheel again to resume the search for decays of


The Chemistry of Superheavy Elements



Even though the OLGA technique has very successfully been applied in gas phase chemical studies of elements Rf through Bh‚ the overall efficiency (including the detection of a two member decay chain) was only about 4%‚ too low to continue studies at the picobarn cross section level. Obviously‚ the large number of steps involved‚ each having a yield below 100%‚ lead to a poor overall efficiency. These include thermalization of the recoil products in a gas‚ attachment of products in ionic or atomic form to the surface of aerosol particles‚ transport of these particles through capillaries‚ heterochemical reactions of the attached species with reactive gases to form volatile compounds‚ gas adsorption chromatography of the compounds with the surface of the chromatography column‚ re-attachment of ejected molecules to new particles followed by a transport to the counting device and‚ finally‚ deposition of the particles on thin foils via impaction. Therefore‚ it would be advantageous to perform the chemical synthesis of the volatile molecule in-situ in the recoil chamber. This approach has already been used in the very first chemical studies of transactinides‚ see Section 4.3. Chlorinating and brominating agents were added to a carrier gas in order to form volatile halides of the 6d elements. However‚ in these early experiments only tracks of SF events were revealed after completion of the experiment. Obviously‚ such a technique has the disadvantage of not

4. Experimental Techniques


yielding any on-line information during an ongoing experiment. Moreover‚ most isotopes of transactinide elements decay primarily by emission. For studies of element 108 (Hs) and element 112 the new device named Insitu Volatilization and On-line detection (IVO) was developed [124]. By adding to the He carrier gas‚ volatile tetroxides of group-8 elements were formed in-situ in the recoil chamber. A quartz column containing a quartz wool plug heated to 600°C was mounted as close as possible to the recoil chamber. The hot quartz wool served as an aerosol filter and provided a surface to complete the oxidation reaction. For future studies with element 112 pure He or even a reducing He/H 2 mixture can be employed. In order to efficiently detect the nuclear decay of isolated nuclides as well as to obtain chemical information about the volatility of the investigated compounds a completely new technique was devised. This new development is cryo thermochromatography of very volatile species on positive implanted N-type silicon (PIN) diode surfaces that allow and SF spectrometry [80]. The carrier gas containing volatile atoms (i.e. At‚ Rn‚ Hg) or molecules (i.e. is flowing through a narrow channel formed by a series of planar silicon diodes. Along this channel a longitudinal negative temperature gradient is established. Due to the close proximity of the silicon diodes facing each other‚ the probability to register a complete decay chain consisting of a series of decays is rather high. A first Cryo Thermochromatographic Separator (CTS) was constructed by U. Kirbach and coworkers [80] at the Lawrence Berkeley National Laboratory. A schematic of the experimental set-up used in the first successful chemical identification of Hs as volatile tetroxide is shown in Figure 12.


The Chemistry of Superheavy Elements

In the actual Hs experiment [30] an improved version namely the Cryo OnLine Detector (COLD) was used. This detector was constructed at PSI and consisted of 2 times 36 PIN diodes. A schematic of the COLD is shown in Figure 13.

4. Experimental Techniques


The COLD featured a steeper temperature gradient and reached a lower end temperature of -170 °C. Two PIN-diodes mounted on ceramic supports were glued together facing each other. Two T-shaped spacers made from silicon confined the gas flow to the active surface of the diodes. The gap between the PIN diodes in the COLD was reduced to 1.5 mm, increasing thus the detection efficiency. The PIN diode sandwiches were enclosed in a coated copper bar, which was placed in a stainless steel housing that was purged with dry The copper bar was heated at the entrance side with a cold finger. The thermostat to +20 °C and cooled at the exit with a liquid emitted by a species geometrical efficiency for detecting a single adsorbed inside the detector array was 77%. The detectors of the COLD array were calibrated on-line with and its daughters and using a source.

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132.4. Experimental Techniques 155 Index Adsorption AIDA ARCA 137‚ 140‚ 144 132 130‚ 131‚ 132 Cryo thermochromatography 145‚ 146‚ 147 CTS 145 BGS 127‚ 134 Bismuth (Bi‚ Z=83) 119‚ 129‚ 130 Bohrium (Bh. 130. 129. Z=107) 135‚ 141‚ 142‚ 144 Chemical separation 117‚ 118‚ 119‚ 120‚ 121‚ 125‚ 126‚ 127‚ 128‚ 129‚ 130‚ 131‚ 132‚ 133‚ 134‚ 135‚ 137‚ 138‚ 141‚ 142 Automated 120‚ 128‚130‚ 131‚ 132‚ 135 Contaminants 119‚ 120 120‚ 127‚ 132‚ Continuous 133‚ 134‚ 135‚ 138‚ 141‚ 142‚ 143‚ 144‚ 145‚ 147‚ 150 Distribution coefficients 129 Extraction 128. Decay chain 120‚ 142 Deposition temperature 137 Detection 117‚ 119‚ 120‚ 127‚ 128‚ 129‚ 130‚ 134‚ 135‚ 137‚ 141‚ 142‚ 143‚ 144‚ 145‚ 147 Detection system COLD 146‚ 147 CTS 145 MG 142‚ 143 ROMA 141‚ 142‚ 143‚ 153 Detector Liquid scintillation 134 Mica fission track 140 PIN diode 145‚ 146‚ 147 PIPS 132‚ 142 Dubnium (Db‚ Z=105) 118‚ 119‚ 127‚ 128‚ 129‚ 130‚ 132‚ 133‚ 135‚ 141‚ 142 133 Liquid-phase 129‚130‚ 135 128‚ 129‚ 130‚ 131 Manual 117‚ 119 One-atom-at-a-time 119 Selectivity Single atom chemistry 117‚ 119‚ 120‚ 141 Speciation 120 Speed 118‚ 128‚ 130‚ 142 Three-column 132 Chemical transport reaction 118‚ 126‚ 134‚ 141‚142‚ 143‚ 144 146‚ 147 COLD 121‚ 125 Compound nucleus 147 Copper (Cu‚ Z=29) Element 110 119 Element 112 119‚ 135‚ 136‚ 145 Element 114 135 Enthalpy of adsorption 137 Enthalpy of sublimation 126 Gas-jet 126‚ 127‚ 128‚ 129‚ 130‚ 131‚ 133‚ 134‚ 141 Aerosol 123‚ 126‚ 127‚ 133‚ 141‚ 142‚ 143‚ 144‚ 145 Capillary 122‚ 126‚ 127‚ 135‚ 141‚ 142‚ 146 Carbon aerosol 126 KCl aerosol 126‚ 127 Mean mobility diameter 126 aerosol 126 . 133‚ 134 135 Gas-phase Impurities 119‚ 122 Ion exchange 130. 131.

Number concentration Group 6 elements 126 142 Hafnium (Hf‚ Z=72) 140‚ 141 135‚ 142‚ 144 Halides 122‚ 139‚ 140 Chlorides Hassium (Hs‚ Z=108) 135‚ 136‚ 145‚ 146‚ 154 142 HEVI 142 HITGAS 136‚ 144‚ 145 In-situ Isothermal gas chromatography 136‚ 137‚ 138‚ 141 145 IVO Kineamtic separator 117‚ 118‚ 119‚ 120‚ 127‚ 130‚ 134 Lawrencium (Lr‚ Z=103) 128‚ 133 119‚ 130‚ 144 Lead (Pb‚ Z=82) Mercury (Hg‚ Z=80) MG Nuclides 141 118 142 129‚ 142 127‚ 134 129 143 128‚ 129‚ 141‚ 142 129‚ 133 143 143 145 142‚ 143 146 OLGA 135‚ 141‚ 142‚ 143‚ 144 .156 The Chemistry of Superheavy Elements Platinum (Pt‚ Z=78) 129 Polonium (Po‚ Z=84) 119‚ 129‚ 130 Production rate 119‚ 121‚ 124‚ 130‚ 132‚ 135 Projectile 121‚ 123‚ 125 118‚ 121‚ 128‚ 129 121‚ 133 118‚ 121‚ 139 118‚ 121‚ 124‚ 146 121 124 Pulsed beam 119‚ 145 Radon (Rn‚ Z=86) 125 Recoil catcher foil 117‚ 120‚ 121‚ Review article 122‚ 136 141‚ 142‚ 143‚ 153 ROMA Rutherford 148 Rutherfordium (Rf‚ Z=104) 118‚ 119‚ 127‚ 128‚ 129‚ 130‚ 132‚ 133‚ 135‚ 139‚ 140‚ 142‚ 144 Seaborgium (Sg‚ Z=106) 130‚ 132‚ 135‚ 141‚ 142 SISAK 127‚ 133‚ 134 Spontaneous fission 118‚ 119‚ 120‚ 135‚ 137‚ 140‚ 141‚ 142‚ 143‚ 144‚ 145‚ 146 Synthesis 118‚ 135‚ 144 Tantalum (Ta‚ Z=73) 131‚ 137‚ 138 Target 118‚ 119‚ 121‚ 122‚ 123‚ 124‚ 125‚ 126‚ 139‚ 140‚ 146 121‚ 123 139 118 118‚ 121 118‚ 121‚ 124‚ 125‚ 128‚ 129‚ 133‚ 146 Gas-jet cont.

4. Experimental Techniques 157 Target cont. 127 Tetroxides 145 Thermochromatography 136. 146 . 118‚121‚129 118 121 118‚121‚ 153 Target preparation 122 Electrospray 122‚123 Molecular plating 122 Plating cell Thickness 121 Vacuum evaporation Target set-up Beryllium window 123 Double-window system 123 123 HAVAR window 124 Rotating targets Supporting grid 123. 141‚ 145 121 Vapor pressure Volatility 140 145. 124.

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The complexes are then chemically characterized by a partition method which can be liquid-liquid extraction. carrier-free radionuclides produced in a nuclear reaction are transported to a separation device by the gas-jet technique and are dissolved in an aqueous solution. The Chemistry of Superheavy Elements. which applies to liquid-liquid extraction. the concentration. Fritz-Straßmann-Weg 2. to repeat the same experiment several hundred or even several thousand times with a cycle time on the order of a minute. cation-exchange or anion-exchange chromatography.). The value is given in its simplest definition. The ultimate goal of the partition experiments is to determine the sovalue. In a chromatography experiment. 159-203. Introduction In the liquid-phase chemistry of the transactinide elements and their lighter homologues. Germany 1. or reversed-phase extraction chromato­ graphy. by the ratio of the activity in the organic phase to that in the aqueous phase. . as we will see below. Universität Mainz. © 2003 Kluwer Academic Publishers. Schädel (ed. the retention time Liquid-phase chemistry is performed mostly in a discontinuous. Recent discontinuous studies 159 M. D-55128 Mainz. in order to get statistically significant results. Kratz Institut für Kernchemie.Chapter 5 Liquid-Phase Chemistry J. as a function of ligand called distribution coefficient. It is then necessary. the latter contains suitable ligands for complex formation. In general. batch-wise manner.V. the distribution coefficient is closely related to the key observable. Printed in the Netherlands.

These discontinuous separations involve a rather time-consuming evaporation step to prepare weightless samples for alpha spectroscopy. the washing was continued. In this hydroxyisobutyric acid pioneering experiment. This is avoided with the continuous ionexchange chromatography with the multi-column technique (MCT). The first two drops (free column volume) contained little or no activity and were discarded. The fast centrifuge system SISAK was coupled with on-line liquidscintillation counting (LSC) and is heading for its first application in the study of transactinides [11. evaporated to dryness and heated to ~500°C to burn off any carbon residue. After the emitting isotope. and a new 6d transition series is predicted to begin with element 104. and some perspectives for further studies.0) onto the top of a 2 mm diameter by 2 cm long heated (~80°C) column of Dowex 50x12 cation-exchange resin. The number. This solution was forced into the resin and. by A. Silva et al. rutherfordium (Rf)). R. lawrencium (Lr). The recoils from the target were stopped in He gas. 2. the 5f series in the Periodic Table ends with element 103. [14] in 1970.J. the was produced by irradiation of 47 of which was electrodeposited over area onto a Be foil with 92­ ions from the Berkeley Heavy Ion Linear Accelerator. The discs were placed active side down directly over detectors.1 Rutherfordium (Rf. pH 4.160 The Chemistry of Superheavy Elements were either performed manually [1-6] or with the Automated Rapid Chemistry Apparatus (ARCA II) [7]. A sketch of the system used is shown in Figure 1. Element 104) FIRST SURVEY EXPERIMENTS According to the actinide concept [13]. more technical details of these experiments are given in Chapter 4. which was first used to study the fluoride complexation of rutherfordium [8-10]. This chapter gives an overview over the chemical separation and characterization experiments of the first three transactinide elements in liquid-phases. layer of the was washed from the rabbit with 50 ammonium (0. 2. were swept out of the recoil chamber through a nozzle. and were deposited on the surface of a rabbit which was coated with a thin After fast transport of the rabbit to the chemistry apparatus. [15] confirmed this placement of Rf in the Periodic Table by conducting the first aqueous-phase separations with a cation-exchange chromatography column and the chelating agent 2-hydroxy-2-methyl-propionic acid). mainly aqueous solutions.1 M. The next four drops (taken in two-drop fractions) were collected on platinum discs. energy and time distribution of Si(Au) . discovery of a long-lived (65-s) Ghiorso et al. the chemical properties which were obtained.12]. after adding more eluant.

spectra were recorded for four sequential one-minute decay intervals from sources after chemical separation. . representing a pair of correlated mother and daughter mother-daughter correlations is consistent with decays.2 to 8.4 MeV. and Cm did not elute in over 100 column volumes. counting geometry and chemical losses. These data [15] show unambiguously that the chemical behavior of the is entirely different from that of trivalent and activity assigned to divalent actinides but is similar to that of Zr and Hf as one would expect for the next member of the Periodic Table following the actinide series. as well as the alkaline earth elements. In contrast. was retained even stronger on the resin. only about 1/10 of this number of events were observed after chemistry due to decay. Approximately 100 atoms of were produced in several hundred experiments. trace quantities of the 3+ ions Tm.5. The average time from beam off to the start of counting was ~60 s. however.4 MeV energy region within a time interval of one minute. two events occurred in the 8. Liquid-Phase Chemistry 161 particles with energies between 6 and 12 MeV emitted by the sources were recorded. These contained 17 events in the energy region 8. Cf. Approximately one half of these events are due to the decay of 26-s the daughter of In two experiments. The overall yield of tracer quantities of the lighter homologues Zr and Hf recovered in drops 3-6 was about 50%. This number of the counting geometry used.2 to 8.

Silva et al. to prepare spectroscopy. one in the feed fraction (12 M HCl). and to do chemical manipulations rapidly.J. is typical for many liquid-phase experiments performed later. Only six events were observed in over one hundred experiments.K. [17] testing the chloride complexation of Rf made use of computer automation to perform all sources. in which chloride complexation is less favored. Again. i. it has not yet been efficient enough to measure values. within the last ~15 years. It also includes the preparation spectroscopy by evaporation of the aqueous effluent of sources for from the column to dryness and it records energy and time of the events and of correlations for unambiguous isotopic assignment of the activity. It combines a fast transport system for transfer of the activities from the target-recoil chamber to the chemistry system with a discontinuously performed chemical separation that is repeated hundreds of times. which thereby avoided the hydrolysis reaction possible at lower acidities. The percentage of Hf in these same fractions was 12%. An extraction chromatographic method was chosen to investigate chloride complexing in high concentrations of HCl. two in elution fraction 2 (6 M HCl). and 29%. it compares the behavior of a transactinide element with that of its homologues under identical conditions. including the actinides. since anionic-chloride complexes formed in the aqueous phase are strongly extracted into this ammonium compound. These results showed the chloride complexation of Rf is consistently stronger than that of the trivalent actinides and is similar to that of Hf. Figure 2 shows the atoms of observed by decay in three sequential elution fractions. are not appreciably extracted.e. even though being “historical”. However. . group-2. The extraction columns contained an inert support loaded with trioctyl­ methylammonium chloride. and three in elution fraction 3 (6 M HCl). Above all.162 The Chemistry of Superheavy Elements The Rf experiment by R. Another first-generation experiment by E.. whereas group-1. Thus. This has only been achieved with improved techniques that have been developed more recently. Such complexes are formed in 12 M HCl by the group-4 elements and are extracted. and group-3 elements. Hulet et al. these latter activities were eluted from the column with 12 M HCl while Zr and Hf. and Rf were extracted and subsequently eluted with 6 M HCl. 59%. no value was determined in this “early” experiment. [15].

Liquid-Phase Chemistry 163 2. see [18-26] for recent reviews. A series of manually performed aqueous solutions was performed by the Berkeley separations of group at the Berkeley 88-Inch Cyclotron [2-6.5. Their experiments involving liquid-liquid extractions typically comprised the following steps: .27].2 DETAILED STUDIES A renewed interest in studying the chemical properties of the transactinide elements in more detail both experimentally and theoretically arose in the late 1980s.

thus defining an extraction sequence Zr > Rf > Hf for the group-4 chlorides. Th. As some of these extraction experiments suffered from differences in the details of the chemical procedures applied to the different elements. K. Hf and Ti. C. was picked up with of the aqueous phase and was transferred to a 1 mL centrifuge cone of the organic phase. Hf. and Th.164 The Chemistry of Superheavy Elements A He(KCl)-jet transportation system was used for the transfer of the activities. The KCl aerosol with the reaction products was collected by impaction on a Pt or TeflonTM slip for 60 or 90 s. [3] performed a series of liquid-liquid extractions and with tributylphosphate (TBP) in benzene to study the effect of HCl.D. -ion concentration between 8 and 12 M on the extraction of and It was found [3] that Rf extracts efficiently as the neutral tetrachloride into TBP from 12 M HCl like Zr.R. Such a behavior is not exhibited by Zr and Hf. leading to the formation of Extraction studies at a constant concentration of 12 M showed that Rf extraction is sharply increasing with increasing -concentration between 8 M and 12 M [3]. Th. The organic phase was transferred to a glass cover slip. [5] performed some additional chloride extractions into TBP/benzene with Zr. and Pu. Czerwinski et al. chloride concentration was varied at a constant Above 10 M concentration. This procedure took about 1 min. Extraction of Rf increased from 60 % to 100 % between 8 M and 12 M HCl. different contact times and volumes used. and Pu while the extraction of Hf was relatively low and increased from 20 % to 60 % between 8 M and 12 M HCl. 2. Hf.1 Hydrolysis versus halide complexation – studies using liquid-liquid extraction techniques Liquid-liquid extractions with triisooctyl amine (TiOA) from 12 M HCl [2] confirmed the results of [17]. e. Kacher et al. and [18] which is not extracted into TBP. The phases were mixed ultrasonically containing for 5 s and were centrifuged for 10 s for phase separation. Hf. and resembled that of This was interpreted in terms of stronger chloride complexing in Rf than in Zr.g. the extraction of Rf decreased and behaved differently from Zr. it was important to confirm these very interesting and somehow unexpected findings in experiments that establish identical conditions for all homologues elements including Rf. A distribution coefficient for Rf between those of the tetravalent pseudo homologues Th and Pu indicated [27] that the hydrolysis of Rf is less than that for Zr.2. The reported low extraction yields of Hf by . Surprising results were obtained when the concentration of 8 M. Cationic species were investigated [27] by extraction into thenoyltrifluoroacetone (TTA). was evaporated to dryness on a hot plate. and was placed over a passivated ion-implanted planar silicon detector (PIPS).

This decrease was observed by A. sequence of extraction into TBP/benzene from around 8 M HCl as Zr > Hf > Rf > Ti. The hydrolysis of a cation is shown in the following reaction On the left hand side of Equation 1. In a parallel study of liquid-liquid extractions into TBP/benzene from HBr solutions. a similar loss of Rf due to adsorption in the Czerwinski et al. and Rf on cobalt ferrocyanide surfaces. As. in general. The extraction behavior of the group-4 elements into TBP from both HCl and HBr solutions was primarily attributed to their different tendencies to hydrolyze [5].R. (They actually conducted their subsequent experiments with polypropylene equipment because only negligible adsorption was observed with polypropylene surfaces. These ferrocyanides are known to be selective sorbents for heavy univalent cations such as and However.) The Hf results from the Czerwinski et al. cation. Czerwinski et al. based on their new Zr-. on the cations are essentially not sorbed by ferrocyanide surfaces. the stronger hydrolysis of the larger size Rf ion is very surprising and in conflict with the results presented in [27]. suggested a revised. extraction of Rf was found to be low and was only increased for bromide concentrations beyond 9 M [5]. establishing seemingly a hydrolysis sequence Rf > Zr > Hf. Hf.5. some ferrocyanides such as Co ferrocyanide have been found to exhibit also particularly high affinities for tetravalent elements such as and involving the formation of a new ferrocyanide phase between the cation and the anion. experiments [3] were based on on-line data taken at the 88-Inch Cyclotron where the activity was collected on a teflon disc which according to [5] accounts for the seemingly low Hf extraction. below 1 M HCl for Zr. [5] who reported that they observed that significant amounts of Hf (more than 50 % in some cases) stick to Teflon surfaces. [4] who studied the sorption of Zr. and below 0. Surprisingly. the onset of hydrolysis at decreasing HCl concentration in the aqueous phase will be reflected by a rapid decrease of the sorbed activity. suggested as an explanation that the coordination number CN (x in . Bilewicz et al. and Ti-results and on the old [3] Rf results. we have the hydrated right hand side the first hydrolysis product being a cation. A. Liquid-Phase Chemistry 165 K. and so the latter authors. still questionable. Th. Bilewicz et al. The latter statement refers to concurrent work by A. Bilewicz et al. hydrolysis increases with decreasing radius of the cation.D. [3] could not be reproduced by C.5 M HCl for Hf.. Kacher et al. Hf-. work [3] was not suspected by Kacher et al. [4] below 3 M HCl for Rf.

respectively. This gives the extraction sequence Zr > Rf > Hf. [28] have determined distribution coefficients of these elements from HCl solutions. one has to consider the difference in total energies of the (partially) hydrolyzed species on the left (It is hand side of Equation 2 that are not extracted and the extractable assumed that the containing species will not extract into the organic .6 x 8 mm columns filled with TBP on an inert support. that for Hf 64. For example.30] of complex formation and the concurrent hydrolysis of complexes To predict the equilibrium constant of Equation 2. the contact time of the aqueous phase with the ferrocyanide surface was only 10 s in the Rf experiments. a value of 150 was determined for Rf in 8 M HCl. Günther et al. and Rf from 8 M HCl into TBP. In view of the somewhat unsatisfactory situation with the conflicting Hf results in [3. the authors found that Zr and Hf sorbed within 20 s and 40 s. R. [28] have shown that this does not withstand a critical examination. This difference makes possible a chromatographic separation of Hf from Zr in ARCA II on 1. In 8 M HCl. within the 10 s interaction of the aqueous phase in the Rf experiments. A study of the extraction of fluoride complexes of and into TiOA was also reported by C. Hf. however no quantitative assessment of the extraction yield or value is made. and from the distribution of the Hf and Zr fraction. Günther et al. It is conceivable that. Consequently. This separation was also studied with the short-lived from the reaction yielding in agreement with the above results from batch extraction experiments. 78-s was produced in the reaction at the Philips Cyclotron of the Paul Scherrer Institute between (PSI).166 The Chemistry of Superheavy Elements Equation 1) for and is 8. Such a sequence is expected from theoretical considerations [28. the conclusion in [6] that the extraction into TiOA for the is not group-4 elements decreases in the order reproducible. [6]. Kacher et al. This work presents some evidence for extraction of into TiOA from 0. and changes to CN = 6 for Rf due to orbitals unavailable for ligand bonding of relativistic effects making the water molecules.5] and with the intention to establish an independent set of data characterizing the extraction sequence of Zr. no equilibrium was established thus making the Rf data meaningless. while Th required more than 90 s to achieve nearly complete sorption [4].D.5 M HF. In a kinetic study. Villigen/Switzerland. It is the author’s opinion that some experimental deficiency and not the increased tendency of Rf to hydrolyze produced the surprising results [4]. However. the of Zr is 1180.

Ta.30] is of opposite order to the hydrolysis of cations [29].2. [35.10]. For both group 4 and 5. and Rf) have shown that the compounds are very similar which can also be supposed for Knowing the analogy in the electronic structure of the halides and oxyhalides of groups 4 and 5 [34. actinides produced directly in the reaction were removed from the solution.29-31].36]. the order of complex formation described by equilibria similar to the reaction (2) in 4-12 M HCl solutions was found to be Pa > Nb > Db > Ta in excellent agreement with experimental data [33] to be discussed in Section 3. This shows that the statements in [5. For these elements. such a sequence is in full agreement with experimental data for Zr. was transported on line to the chemistry apparatus. Szeglowski et al. For group 5. and Db [30]. which allows determining the differences in the Coulomb and the covalent parts of the binding energy separately. the hydrolysis of complexes [26. Hf. [9. G.studies using ion-exchange resins Fluoride complexation of group-4 elements was studied by Z. Pa. presumably as while the following cation-exchange column retained its cationic decay products. [9. (2) as it was found for the corresponding group-5 elements. presently using the DS DV method [26.5. and Rf are still to be done. Pfrepper et al. Calculations for Zr. Hf. one can postulate the same order of complex formation Zr > Rf > Hf according to eq.2 Hydrolysis versus halide complexation -. In the work of [8]. and by E.2 M HF in a degassing unit. Their detection was proof that Rf forms anionic fluoride complexes which are sorbed on an anion-exchange resin. and Nb. In the first cation-exchange column. but one can already draw qualitative conclusions based on a parallel study of the hydrolysis of chloro complexes of the group-5 elements Nb. 2. Ta. Reasons for this are dominant differences in the Coulomb part of the free energy of reaction when groups are replaced by anions. the longlived descendants and were desorbed from the third column and detected off-line by spectroscopy.10] have developed this technique further. thereby making it a quantitative technique capable of measuring distribution coefficients In the conventional off-line chromatography as performed . Liquid-Phase Chemistry 167 phase because of the strong hydrogen bonding interaction between and This can be done by quantum chemical calculations. and the solution was passed through three ion-exchange columns. respectively. was continuously dissolved in 0. After the end of bombardment. Hf.6] concerning the seemingly low extraction of Hf and Rf as being due to an increased tendency of their cations to hydrolyze are completely misleading. was sorbed. Pfrepper et al. In the next anion-exchange column. [8]. showing that compounds of the 5d elements are more hydrolyzed than those of the 4d elements and are hence less extracted. by G. Strub et al.26]. Earlier calculations [33] of (M = Zr.

As in [8].168 The Chemistry of Superheavy Elements by ARCA II..27 M HF/x M obtained in the same system with the MCT technique. first a cation-exchange column that retains the from the continuously flowing feed solution. firstly. [9] have verified the equivalence of Equations 3 and 4. one gains the possibility of a continuous on-line mode over many onto the anion-exchange column is performed hours. is abandoned This and replaced by the detection of its long-lived descendant. values for Hf isotopes obtained. three ion-exchange columns are used in series. the detection of the transactinide isotope itself. As in [8]. The longthat are formed by radioactive decay of lived decay products during its retention time on the anion-exchange column are eluted from this column as cations and are fixed on the following cation-exchange column. the distribution coefficient is determined via the retention time (elution position) as with time. in batch They compared experiments and by conventional elution chromatography in the anionexchange system HS36 ( a resin with the quaternary triethyl-ammonium (x variable) with . The part of the that survives the retention time on the anion-exchange column is eluted from it and passes the following cation-exchange column to be subsequently collected in a reservoir in which it decays into the long lived decay products and are isolated separately after the end of the on-line experiment and assayed off-line for of From the ratio of and and the nuclear half-life of one obtains the distribution coefficient G. secondly. 20-d way. one is using the nuclear half-life as an internal clock.e. In order to determine the ionic charge of the Hf by . Similarly half-life to the principle used in the on-line isothermal gas chromatography. This is necessary as could be produced directly by transfer reactions. They used the shortlived Hf isotopes and detected the daughter nuclides and spectroscopy. The feeding of under conditions in which the retention time is on the order of the nuclear i. values group) – 0. values on the order of 10-50 are selected [9]. V = flow rate of the mobile phase and M = mass of the ion exchanger (g). It follows the true chromatographic column (C) filled with an anion-exchange resin. Pfrepper et al. hold-up time due to the free column volume.

1) M sorbed the descendants 23-s 3-d and 20-d contained 50 mg of the strongly acidic cation exchanger Wofatit KPS. Assuming the same conditions for their experiment [10]. [9] had shown previously that.27 M HF and 0. values for trivalent rare mL/g resulting in a breakthrough volume in excess earth cations exceed of 500 mL . and 2.2 (0.35 mL The cation-exchange column(s) that of 0. In the application of the MCT technique to G. it was decided to renew the cation-exchange columns collecting the descendant fractions and every 12 h. Thus.4 for the fluoride complex of Hf as determined from the slope of the plot of versus the logarithm of the concentration of the counter ion. Pfrepper et al. This is evidenced also by Figure 3 concluded that Hf probably forms values obtained by the on-line MCT technique are compared in which the with those from a series of batch experiments performed in parallel with the same anion.2 M mL/g with 0. it was concluded that with the MCT technique.3 M.4 ± 0. Liquid-Phase Chemistry 169 fluoride complexes. for concentrations < resin.5 M corresponding to an ionic charge of –1. For the similar cation-exchange resin Dowex 50x12. From the good agreement.8 values were found to be 12.7 ± 1. . used about 20 mg (11 mg) of the anion-exchange resin HS36 in the chromatographic column at an elution rate of approximately 0.8 mL/g with 0. Pfrepper et al. This corresponded to eluent volumes of about 260 mL while the breakthrough volume was estimated to be about mL. at first sight. the concentration of the counter ion was varied. determination of the ionic charge of complexes of transactinides must be feasible. G. breakthrough of the cationic “daughter nuclides” was safely prevented.5. From this it was .9 ± 0.

5 M HF/0. The elution of Th from the resin is observed at more than one order of . It is impossible to reconstruct what this did to the values in values of Hf and [10].5 M HF/0.05 M HF/0.1 M respectively. compatible with an ionic charge of the fluoride complex of –1. the breakthrough volume for lanthanides and actinides in the experiments by G.1 M and 500 in 1 M HF/0. A. below M HF. where indistinguishable Rf were reported.9 ± 0. Thus. [36] have observed that the values of trivalent lanthanide and actinide cations in mixed HF/0. The value in 0. the stoichiometry characteristic a close homologue of Hf and forms of Hf and other group-4 elements. Kronenberg et al.8 and 47 were determined in 0.27 M HF/0.1 M A simultaneous rise of values on the anion-exchange with values resin Dowex 1x8 is observed [36] for >0.27 M HF/0.170 The Chemistry of Superheavy Elements and were produced simultaneously by irradiation of a and with ions at the Dubna U-400 combined target of Cyclotron.1 M on a strongly acidic cation-exchange resin can be estimated to be on the order of 800.1 M reaching 170 in 0. Strub et al.1.1 M respectively.36] do cast doubt on the values for Hf and validity of the results in [10].1 M solutions on the cation-exchange resin Dowex 50Wx8 exceed M.1 M and 2500 in 1 M HF/0. both the Hf and the Rf descendants were breaking through the cation-exchange columns in less than 2 h. i. the values decrease to 2000 in 0.1 M HF/0. For of its the were evaluated yielding values of about 14 and 50 in descendant 0. [10] was not >500 mL but rather <40 mL. The behavior of Zr and Hf is very similar (Hf sticking to the resin even at slightly higher HF concentrations). Hf. and Th are > indicating the presence of cations.1 M On the cation-exchange resin. giving an ionic charge of –1. [35] have investigated in batch experiments values of the long-lived tracers and on a strongly acidic cation-exchange resin.e.2 M and 0. E.2 M and 0. In the and the nuclides spectra of were detected as the decay products of and values on the order of 14. It was concluded [10] that Rf has properties of .27 M HF/0.27 M HF/0. Pfrepper et al.27 M HF/0. Häen) in 0.1 M HF/0..05 M HF/0. In the range < [HF] < M. however.1 M 700 in 0. the significant differences between the Rf in mixed solutions observed in [35. the values for Zr.1 M 1300 in 0.85 ± 0. the values of Zr and Hf decrease due to the formation of neutral or anionic fluoride complexes. Aminex A5.1 M 1600 in 0. and on a strongly basic anion-exchange resin (Riedel-de solutions containing variable concentrations of HF.1 M thus indicating that anionic fluoride complexes are formed. For higher HF mL/g only for HF concentrations below concentrations.2.

and mass of the resin . This fraction was fraction of 200 prepared as sample 2. On an anion-exchange resin. Liquid-Phase Chemistry 171 magnitude higher HF concentrations. collected and loaded onto the anion-exchange column as in the experiments with the cation-exchange columns. Hf. As is shown by Figure 4. there is little sorption of Zr. values are often calculated as follows: with As specific activity in the solid phase [Bq/g].1 M M HF was collected to strip all group-4 elements from the column. In the Rf experiments [35] performed at the PSI Philips resin. the effluent was evaporated to dryness as sample 1. the sorption on the anion-exchange resin stays low for all HF concentrations indicating that Th does not form anionic fluoride complexes. In order to elute remaining Rf and Hf from the column. UNILAC accelerator where shortlived Hf isotopes were produced in xn-reactions of a beam target.5. i. activity in the liquid phase [Bq]. volume of the solution [mL]. activity in the solid phase [Bq]. This shows that the disappearance of the cationic species at low HF concentrations is followed immediately by the formation of anionic fluoride complexes. Again. In the range values of Zr and Hf in batch experiments rise simultaneously. Darmstadt. Rf and Hf were transported. as expected. The target contained 10% Gd enriched in to produce simultaneously short-lived Hf isotopes that were used to monitor the behavior of Hf and to perform yield checks by spectroscopy. These off-line data were compared with on-line data taken with ARCA II at the Gesellschaft fur Schwerionenforschung (GSI). was produced in the reaction at 100 MeV. a second fraction of 200 0. In the anion-exchange experiments.e. The deposit was dissolved in 200 0.. The fraction was prepared as sample 2. in the same range as they decrease on the cation. see Figure 4. there is general with an enriched agreement between both sets of data. Rf and Hf were transported by a He(KCl) gas jet and were collected for 90s by impaction inside ARCA II [7]. the and Th at low HF concentrations.6x8 mm cation-exchange column at a flow rate of 1 mL The effluent was evaporated to dryness as sample 1. specific activity in the liquid phase [Bq/mL]. In order to elute remaining Rf and Hf from the column. For Th.1 M M HF (x variable) and was fed onto the 1. a second 5 M M HF was used.

The values for at 5· M HF and at M HF are lower limits as no decays were detected in sample 1. at one order of magnitude higher HF concentrations than for Zr and Hf.. in elution experiments Equation 5 yields only correct values for the fortunate situation of equal activities in fraction 1 and 2. The values using Equation 5 are obtained such that the activity of sample 1 is attributed to the liquid phase and the activity of sample 2 to the solid phase.1 M HF. cuts between fraction 1 and 2 at the maximum position of the elution values shown in Figure 4 were curve.172 The Chemistry of Superheavy Elements [g].. While the off-line data for Hf clearly indicate that anionic . the free column volume. The on-line data for Hf are consistent with the off-line data.e. Under the given conditions. the value is varied until the experimentally observed activity in fraction 1 results. i. the behavior of Rf is intermediate between that of its pseudohomologue Th and that of its group members Zr and Hf.e. However. It is seen that the decrease of the values for Rf occurs between 0. The results of the on-line experiments with Rf and Hf on cation-exchange columns are given in Figure 4 together with the results of the off-line batch experiments. The number of theoretical plates – obtained from the shape of tracer elution curves -. calculated by a computer program that simulates the elution process. In an iteration process. the volume of fraction 1 and an assumed Kd value are the initial input parameters.01 M HF and 0. The results of the on-line experiments with the anion-exchange columns are given in Figure 5. To circumvent this deficiency. i.

1 M and 0. Seemingly.8. there is no indication of a maximum values for Rf.10] that there are no anionic fluoride complexes for Rf at any HF concentration.05 M thus varying the concentration of which acts as a counter ion competing for the binding sites on the anion exchanger. Liquid-Phase Chemistry 173 fluoride complexes of Hf are formed for one observes that the Hf data taken on-line are systematically lower. The reason for this discrepancy is unknown at this time. Even for 1 M HF. which is about two orders of magnitude higher than the concentration from whereon values are observed for Zr and Hf. A possible influence of the kinetics on the differences between on-line and off-line data remains speculative at the moment. It was observed [35] that the values of Hf and Rf rise with decreasing concentration indicating that negatively charged complexes are formed both for Hf and for Rf. but that the counter ion is much more effective in removing Rf from the binding sites on the anion exchanger than in removing Zr and Hf. This was the starting point for a new series of experiments with anionand the HF exchange chromatography with Aminex A27 in which the concentration were varied systematically [36]. rise in the As it would be in contradiction to the results in [6. the behavior of Rf is different from that of Zr and Hf – if compared with the off-line data .as there is almost no sorption of Rf on the resin. the concentration of was varied [35] between 0.5.01 M at a constant HF concentration of 0. The following observations were made: .

and column C with 17 mg of Dowex 1x8 in the fluoride form. columns F and D were filled with 68 mg Dowex 50Wx8 and used for 4 h. M In the second experiment.5 M HF/0.1 see Figure 5. In the first case. performed in pure 0. the values for Hf and Rf are equally high at The latter observation suggested that the counter ion acts with a remarkable selectivity for the Rf-fluoride complex. This leads to . and that appreciable anion exchange occurs only when the hexafluoride anion is formed.1 M was performed to corroborate the low values obtained in [35] with ARCA II on an anionexchange resin. makes this statement possible. but not with the value in 0. Each experiment was run for 24 h at an average beam intensity of The first experiment with 0. A second counter ion discussed in [36] is the -ion. The insensitivity of the values of Rf to the actual HF concentration in 0. Column C was filled with 50 mg of the anion exchange resin Dowex 1x8 in the nitrate form.5 M HF/0. One might speculate that the the is very if formed in the same concentration range as effectively replaced by the counter ions. Taking zero to be compatible with 3 events at 95% confidence level in Poisson statistics. respectively. In the second case.27 M HF/0.174 The Chemistry of Superheavy Elements The dependence of the values of Rf on the concentration at fixed HF concentration (0. We note that in [36] there were also two MCT experiments performed with using 0. In the absence of . If values of Hf and Rf are plotted one observes the versus the ratio of concentrations following: The values of Hf rise between and and reach a plateau and There is a second rise between and followed between by a second plateau. see Figure 5. One might speculate that the two steps reflect the subsequent formation and anion exchange of and The values of Rf stay low until from where on they rise and reach the same level as values of Hf in the second plateau.05 M) is much more pronounced than that for the values of Hf.1 M and 0.01 M HF without any 90 events attributable to were observed in the strip fraction representing the solid phase and zero events in the liquid phase. leads to an upper limit for the value of Rf of <3 which is rather consistent with the data in [35].01 M HF. A total of 80 decays were observed in the sample 1 representing the liquid phase and no attributable to event in the strip fraction representing the solid phase. the cation-exchange columns F and D were filled with 330 mg of Dowex 50Wx8 and were used for 3 h to prevent breakthrough of the cationic descendants.1 M in [10].

1 M and high.01 M HF. Element 105) FIRST SURVEY EXPERIMENTS First studies of the aqueous-phase chemistry of element 105. The potassium chloride spot on the glass plate was fumed with 3 of 15 M nitric acid. it was estimated that the time interval from 0 s to 140 s contained ~2 background events from longer-lived activities. Gregorich et al. The average time from the end of accumulating the aerosol on a glass plate to the beginning of counting for and spontaneous fission (SF) decays was 51s. When the second fuming was performed with 7 second drop of nitric acid had dried.70 MeV were observed during the first 140 s of counting (~ 4 half-lives of By looking at the time distribution of events in this energy range out to 500 s.39] at around 100 MeV with a cross section of a few nb. They corroborate the so far unexplained finding that sorption of the Rf fluoride much more anions shows an extreme sensitivity to the presence of pronounced than the respective sensitivity of H f .. 3. in 0. 801 adsorption experiments were performed in [37]. 3.42 to 8. The decontamination from actinides was very good.01 M HF. The glass plate was immediately dried in a stream of hot air from an electric ‘heat gun’ and placed over one of the Si(Au) surface barrier detectors.1 Dubnium (Db. Liquid-Phase Chemistry 175 a lower limit for the value on the order of 300 compatible with the one measured with ARCA II in pure 0. are consistent with the ones determined with ARCA II. A total of 26 events in the energy range from 8. In the bombardments. a of 15 M nitric acid. low in 0. were conducted manually in 1987 by K. the potassium nitrate and the actinide activities on the glass plate were removed by washing the plate with 1. the glass plate was removed from the collection site and was placed on a hot plate. The isotope 34-s was used which is produced in the reaction [38. one can state that the i. After this nitric acid dried. Any remaining dilute nitric acid was removed by washing the glass plate with acetone from a second squirt bottle. As it was known that group-5 elements sorb on glass surfaces from strong nitric acid [40]. values for Rf obtained with the MCT. dubnium (Db). In summary.5 M nitric acid from a squirt bottle. The decay rates of indicated that only 0.25% of the fermium activities remained on the glass.5 M HF/0.E.5. and comparable to that of Hf. At the end of the 60-s collection time. leaving events due to the decay of or its daughter A spectrum containing . the following adsorption experiment was carried out: The activity bearing aerosol from a He(KCl) gas-jet was collected on a glass plate.e. [37].

For comparison. is presented in Figure 7 for . a summed spectrum of unseparated products from this reaction.176 The Chemistry of Superheavy Elements the data from the first 30 s of counting for all 801 samples is presented in Figure 6. taken with a rotating wheel system for a 20-s interval starting 60 s after the end of collection of aerosols.

as well as ~14 uncorrelated events and ~2 background events. A maximum likelihood fit to the half-life of the 16 singles events which occurred at times shorter than 140 s from the beginning of counting together with the 5 parent events of the mother-daughter correlations gives a half-life of s. it appears that the adsorption yield was probably overestimated by about a factor of 2.E. an remainder of the decay being either by SF or by electron capture to which then decays by SF. The 26 events in Figure 6 attributed to and contain 5 timecorrelated parent-daughter pairs.36 is within the one sigma uncertainty of 0. branch of 51 ± 14% was deduced for with the From this. The other chemical separation attempted in [37] involved the extraction of anionic fluoride species into methyl isobutyl ketone (MIBK).18 consistent with the expected ratio.2 ± 0.5 s.3 ± 0. a large relative enhancement of the activities due to in the adsorption experiments. consistent with the accepted half-life of 34 s. which are produced by interaction of the beam with a small lead impurity in the target.1 M HF as the aqueous phase. There is. Gregorich et al. Liquid-Phase Chemistry 177 comparison. In view of a more recent determination of that cross section [41]. From a detector geometry of 30% of one would expect the ratio of correlated pairs to uncorrelated events to be 0. Figures 6 and 7 and its daughter.8 M . also observed 26 SF decays in the first 140 s of which 23 were assigned to the decay of giving a half-life of again consistent with the known 34 s half-life. It appears that in Figure 6 there is little fractionation between the francium-polonium activities. however.5 nb was estimated based on an estimated adsorption yield of 80%. The measured ratio of 0. An overall production cross section of 3. and MIBK as system with 3. In the adsorption experiments.5. A maximum likelihood fit to the half-life based on the time intervals between parent and daughter events gives s which is also consistent with the accepted value of 4. and the fermium activities.214. demonstrate that insufficient decontamination from polonium can seriously hamper the detection of transactinides. The extraction and 1. K. as indicated in Table 1.

The higher charge would then prevent extraction even into solvents with a relatively high dielectric constant such as MIBK. while niobium is extracted to only a small extent. Thus.1 Liquid-liquid extraction studies from mixed halide solutions While polynegative species cannot be extracted into ketones. 335 extractions were performed.V. tantalum is extracted into MIBK nearly quantitatively. 3.7 MeV nor any fission were observed within the first two minutes of counting. under these conditions.178 The Chemistry of Superheavy Elements the organic phase was chosen because MIBK had been found to be an ideal solvent for the rapid preparation of a sources by evaporation. The phases were mixed ultrasonically for 2 s and containing 20 separated in a centrifuge within 4 s.2 DETAILED STUDIES 3. Kratz et al. In these experiments. it is possible to extract them by anion exchange into high molecular-weight ammonium salts. It was expected that this trend would continue and dubnium would be extracted quantitatively. the MIBK upper phase was pipetted onto a Ni disc which was heated from the edge. After drying. dubnium is not behaving chemically like its lighter homologue tantalum. In tests. Amine extractions have another advantage for chemical studies of species that are produced as single atoms such as so that their chemical behavior must be studied “one-atom-at-a time”. The KCl and the activities were dissolved in 20 of 3. Then the principle of chromatography can be applied to single atoms or ions. No particles in the energy range 8. [42] brought their ARCA II equipment to the Berkeley 88-Inch Cyclotron to perform a large number of automated reversed-phase extraction . Under these conditions. The non Ta-like behavior of Db might indicate that Db forms polynegative anions like under the chosen conditions. and the many adsorption-desorption cycles along the column in the elution of that ion ensure a statistical behavior. the activity-bearing aerosols were collected for 90 s on Pt foils. so that one can be reasonably certain that the observation represents the ‘true’ chemistry of the element. This solution was then placed in a centrifuge cone of MIBK.4 – 8.2. demonstrating conclusively that. the Ni disc was placed over one of the Si(Au) surface barrier detectors. The average time from the end of the aerosol collection to the start of and SF counting was 50 s. in 1988 J.8 M M HF. high molecular-weight ammonium salts are best suited as stationary phase on inert column support materials for High Performance Liquid Chromatography (HPLC). performed with the chemical yield was found to be 75%. In the dubnium experiments. After centrifuging. Due to their high viscosity.

Pa activity into the Ta fraction.6x8 mm columns filled with tri-isoweight ratio octyl amine (TiOA) on an inert support (VoltaefTM. a Nb. Ta. two decays were detected in the acetone strip fraction. On the average. Pa. 88% of the activity (38 events including 4 correlations) were found in the Nb.Pa fraction.Pa fraction was removed from the column with 4 M HCl/0. To this end. Liquid-Phase Chemistry 179 chromatography separations with the 1. Ta. Nb. are shown in the top section of Figure 8. Hf. with no correlated pair) in the Ta fraction.5 particle microamperes. and distinctly different from . extraction into the column material occurred from 12 M HCl/0. and some lanthanides produced on line and transported to ARCA II with a He(KCl) jet. This demonstrates that dubnium behaves similar to Nb. and Pa under the same conditions. In a first series of 207 experiments. In the next series of 721 collection and separation cycles. as shown in the middle part of Figure 8. Elution curves for actinides. and by stripping the amine (along with the extracted activities) from the columns by dissolving the TiOA in acetone. Ta. and 9 events including 1 correlated pair. and 12% (5 events. This distribution is identical with that of Nb and Pa. with carrier-free activities produced on-line. In agreement with earlier tracer studies. extraction into the amine phase events and four SF occurred from 10 M HCl. the activity was adsorbed from 12 M HCl/0. followed by the stripping of Ta from the column with 6 M M HF. Ta. In the beginning of the experiments.02 M HF on the TiOA column as before. there was a tailing of about 10% of the Nb. and Pa also in 10 M HCl. 32 – 63 1:5).02 M HF.02 M HF or from 10 M HCl. and protactinium which were known to extract either from 12 M HCl/0.4 to 0. In a second series of 133 experiments. Nb. chemical yields for Nb. and 12 SF decays were recorded. This time. tantalum. Its extraction was verified by feeding the activities to the columns. it was most important to verify that the dubnium halide complexes were extracted into the TiOA phase under the same conditions as niobium. indicating that forms anionic complexes that are extracted by TiOA. and an assay of the samples for and SF decay started about 45 s after the end of the 60-s collection time. The acetone strip fraction was evaporated to dryness. the effluents from the TiOA mini columns were collected in fractions of three drops in small test tubes and were assayed for activities using two Ge detectors. and Pa were consistently found to be 85 ± 5%. The performance of ARCA II was studied with tracers of Zr.02 M HF. was produced in the reaction at 99 MeV with beam currents of 0.5.


The Chemistry of Superheavy Elements

that of Ta. This shows, in contrast to simple extrapolations, that the trend in the chemical properties in group 5 from Nb to Ta does not continue, but is reversed in going from Ta to Db. The distribution of SF decays between the Nb,Pa fraction (39) and the Ta fraction (10) corroborates the above finding. In a last series of 536 experiments, a separation of Pa from Nb was performed (see bottom part of Figure 8). After feeding of the activities in 10 M HCl onto the column, Pa was eluted first with 10 M HCl/0.025 M HF. Under these conditions, a fraction of the Nb activity begins to break through.

5. Liquid-Phase Chemistry


The change of the eluent to 6 M M HF was timed such that the Pa fraction contained 80% of the Pa and 20% of the Nb, while the Nb fraction contained the remaining 20% of Pa and 80% of Nb. The decays were equally divided between the Pa and Nb fractions: There were 25 events, including 5 correlated pairs, in the Pa fraction, and 27 events, including 5 correlated pairs, in the Nb fraction. The Pa/Nb ratio of SF decays was 25:19. These results indicate that the halide complexing strength in dubnium is between that for Nb and for Pa. The half-lives deduced from the 106 singles, 15 correlations and 109 SF decays were all compatible with the 34-s half-life of and the 4.3-s The total production cross section of at 99 MeV was half-life of 8.3 ± 2.4 nb. In the discussion of the rather unexpected chemical results [42], it was suggested “that the chemical properties of the heaviest elements cannot reliably be predicted by simple extrapolations of trends within a group of elements”, and that “relativistic, quantum chemical calculations for compounds of Nb, Ta, Pa, and Db are needed to understand in detail the differences in the halide complexing of the group-5 elements”. The TiOA column experiments were continued [43] by feeding the activities onto the columns in 12 M HCl/0.01 M HF and eluting a Pa fraction in 0.5 M HC1/0.01 M HF followed by elution of a Nb fraction in 4 M HCl/0.02 M HF. It was found that elutes earlier than the bulk of the Nb activity, i.e., dubnium shows a more Pa-like behavior. From the distribution of the events between fractions 2 and 3 in [42,43] values, or the fractional were estimated in [43] for 10 M HCl/0.025 M Hf, extraction, %p, of 4 M HCl/0.01 M HF, and the newly investigated 0.5 M HCl/0.01 M HF. The results are shown in Figure 9. It is seen that Db shows a striking non Ta-like behavior and that it follows, at all HCl concentrations, the behavior of its lighter homologue Nb and that of its pseudo-homologue Pa. From this similarity, oxygen containing structures or were such as known for Nb and Pa, e.g., discussed also for Db [43], and the preferential formation of oxygen containing complexes of Db was also predicted theoretically[44]. However, in [44], the extraction sequence Pa > Db > Nb was predicted which is the inverse sequence of that observed experimentally, see Figure 9.


The Chemistry of Superheavy Elements

Due to the complicated situation in mixed HCl/HF solutions, with possibilities to form mixed chloride/fluoride complexes or even pure fluoride complexes, it was recommended in [44] to repeat the experiments in the pure HCl system. The original decision of the experimenters to add small amounts of HF to the HCl solutions was recommended in the literature [45] to prevent hydrolysis and ”to maintain reproducible solution chemistry” of the group-5 elements. The proximity in the Db behavior in the TiOA experiments to that of Pa was the reason for performing a series of extractions of Db into diisobutyl­ carbinol (DIBC), a secondary alcohol which is a very specific extractant for Pa. The extraction from concentrated HBr solution in ARCA II was followed by the elution of a Nb fraction in 6 M HC1/0.0002 M HF, and of a Pa fraction in 0.5 M HC1. The number of decays observed in the Nb fraction indicated that less than 45% of the Db was extracted into DIBC, and the extraction sequence Db < Nb < Pa was established [46]. This suggests that the seeming similarity between Db and Pa concluded from the TiOA experiments is not a general phenomenon. 3.2.2 Liquid-liquid extraction studies from pure halide solutions As suggested in [44], the amine extractions of the group-5 elements were systematically revisited by W. Paulus et al. [32,49] in pure HF, HCl, and HBr solutions. V. Pershina [29-31], on the basis of an improved model of

5. Liquid-Phase Chemistry


hydrolysis [29], and by explicitly considering the competition between chloride-complex formation and hydrolysis of the chloride complexes [30] has predicted the extraction sequence in the pure chloride system. She also predicted the extraction sequence fluorides >> chlorides > bromides for the halide complexes of the group-5 elements [31]. For tracer activities of Pa, Nb, and Ta, these predictions were verified experimentally for a number of amines [32,49] in batch extractions. Figure 10 shows an example for the quaternary ammonium salt and aqueous HCl solutions.

Based on these results, new chromatographic column separations with ARCA II were elaborated [32]. In these experiments, most of the amines tested in the HCl system showed slow kinetics for back extraction into the aqueous phase, resulting in elution peaks with an unacceptable tailing of the activities into the subsequent fraction, a feature that was not observed in the mixed HCl/HF system [42]. An acceptable chromatographic separation was only achieved with the quaternary ammonium salt at a flow rate of the mobile aqueous phase of 1 mL/min. Carrier-free tracers of Eu, Nb, Ta, Pa, Zr, and Hf were fed onto the column in 10 M HCl. Zr, Hf, and Ta were eluted in 6 M HCl, Nb in 4 M HCl, and Pa in 0.5 M HCl, see Figure 10. Thus, this system provides conditions for extracting all relevant elements from one HCl
Studies with tracer activities of the lighter homologues.


The Chemistry of Superheavy Elements

solution in a first step and for differentiating between Ta, Nb, and Pa in subsequent elutions. Similarly, new partition experiments and chromatographic separations were performed with the fluoride salt of Aliquat336 in HF solutions and with the bromide salt of Aliquat336 in HBr solutions. The values in the HBr system show the same sequence as in the HCl system: Pa > Nb > Ta. However, the threshold HBr concentrations above which an appreciable extraction is observed are shifted to higher HBr molarities, i.e., to 6 M HBr for Pa, 9 M for Nb, while Ta is not extracted even from 12 M HBr. Chromatographic separations were performed by loading the activities onto the 1.6x8 mm column in 12 M HBr and by eluting Nb in 7 M HBr and Pa in 2 M HBr. The fact that Ta did not extract from HBr solutions made this system the least attractive for an application to element 105. With the fluoride salt of Aliquat336, values on the order of were observed for all tracer activities (Pa, Nb, Ta) and somewhat lower ones for Zr, Hf even at low HF concentrations. The same extraction sequence Pa > Nb > Ta as in the HCl- and HBr-systems was observed at 0.5 M HF. For values stay high for Nb and Ta up to 12 increasing HF concentrations, the M HF while they decrease for Pa, Zr, and Hf due to the formation of polynegative fluoro complexes such as and (M=Zr, Hf), respectively. In chromatographic separations, after feeding the activities onto the 1.6x8 mm column in 0.5 M HF, a Pa fraction was eluted in 4 M HF and Nb and Ta were subsequently stripped from the column with 6 M MHF.
Studies of the dubnium behavior. 930 experiments were conducted with

produced at the Berkeley 88-Inch Cyclotron in the reaction. Extractions were performed in the - HCl system with a 50 s cyclic collection time of the KCl aerosol on a slider in ARCA II. The reaction products were fed onto the column in 10 M HCl followed by the elution of a Ta fraction in 6 M HCl and a Nb,Pa fraction in 6 M M HF. The effluents were continuously sprayed through a 60 nozzle onto hot Ta discs on which they were evaporated to dryness by hot He gas and infrared light. Start of measurement of the activities was 60 s (Ta fraction) and 76 s (Nb, Pa fraction) after the end of collection, respectively. 6 singles in the Ta fraction and 12 in the Nb,Pa fraction were registered with life times compatible with the 34-s half-life of In addition, 3 pairs of correlated mother-daughter decays were registered, one in the Ta fraction and two in the Nb,Pa fraction. From this distribution, a value of ~440 for element 105 in 6 M HCl was deduced [32], see Figure 11. This

5. Liquid-Phase Chemistry


value is much larger than that of Ta (22), smaller or equal to that of Nb (680), and smaller than that of Pa (1440). From this, the extraction sequence was deduced [32] which is in agreement with the theoretical prediction [30].

In the system, 377 experiments were performed with ARCA II. The collection time of the He(KF) gas-jet was 50 s. The dissolved reaction products were loaded onto the column in 0.5 M HF. In elutions with 4 M HF (Pa fraction) and 6 M M HF (Nb,Ta fraction), 4 correlations were detected in the Nb,Ta fraction and none in the Pa fraction. value (Due to a Po contamination, singles were not evaluated.) The resulting from the probability distributions for zero (Pa fraction) and 4 (Nb,Ta fraction) observed correlated events is >570 in 4 M HF which is close to that for Nb and Ta and differs markedly from that for Pa (~19), see Figure 12.

42.31] and experimentally [32.186 The Chemistry of Superheavy Elements To conclude. The studies of the halide complexing of the group-5 elements both theoretically [30.31]. In pure HF solutions. it differs considerably from both Pa and Ta.2. it differs markedly from the behavior of Ta. and Pa are eluted promptly while tetravalent and trivalent metal ions are . In pure HCl solutions. it differs mostly from the behavior of Pa.43] demonstrate the progress that has been made in understanding details of the chemical properties of the transactinides. 3. Elutions from cation exchange columns in ARCA II with unbuffered dilute show that Nb. Ta.3 Studies using ion-exchange resins and an organic complexing agent -­ chemical and nuclear results Another series of experiments with Db used its complexation with the that had been used in the hydroxyisobutyrate first liquid-phase rutherfordium experiment [15]. the amine extraction behavior of dubnium halide complexes is always close to that of its lighter homologue Nb in agreement with the predicted inversion of the trend of the properties when going from the 5d elements to the 6d elements [30. Chelating by depends strongly on the charge of the metal ion [41]. In mixed HCl/HF solutions.

Similar experiments performed at the Mainz TRIGA reactor with confirm this result as shown in Figure 14.5. both activities appear in (9 s). The dissolution of the collected tantalum activity from the frit was investigated as a function of the concentration. 210 In experiments at the UNILAC accelerator at GSI.6x8 mm) which might cause an earlier breakthrough of the tetravalent and trivalent metal ions it was desirable to decrease the concentration.075 M of 0. After the elution of Nb and Pa in 0. the tantalum isotopes were transported by the He(KCl) gas-jet and deposited on a polyethylene frit in ARCA II. Liquid-Phase Chemistry 187 strongly retained on the resin [41].025 M 34 dissolution of >75% of the tantalum activity was achieved in 2 s. Because of the smaller column size in ARCA II (1. The time required for the complete elution of Ta from the column was about 4 s.5 M see Figure 13.7x25 mm column filled with Aminex A6 (particle 0. Even with of 0. This is shown in Figure 13 for manually performed separations of pentavalent Nb and Pa from tetravalent Zr using and a 1.075 M The tracer activities are fed onto the column through a size sample loop. . The first the effluent and are eluted completely in another 150 activity of the tetravalent Zr is detected after the elution of another 3150 Zr can be eluted in (190 s). Darmstadt. After the dead volume of 130 (7 s).

a new column was positioned below the collection frit. the Ta disc was inserted and SF detection.54 and decreased to 0.51 with the remainder of the total thickness being its daughter. As the elution obviously takes more time with 0. The time sequence for the Db separations was as follows: After collection of the transported activities on the polyethylene frit in ARCA II for 1 minute. In the production runs with at the 88-Inch Cyclotron of the Lawrence target was 99 MeV. 114 continuous collection and separation cycles were conducted before the program was stopped. After three separations each.5 s).05 M was finally selected for the dubnium experiment. The Berkeley Laboratory. After flaming and cooling. The He(KCl) gas-jet efficiency was measured frequently during the . Start of into one of ten detector stations for counting was 39 s after the end of collection. the frit was washed with 100 of unbuffered 0. the used magazines were removed.05 M solution (6.0125 M see Figure 14. This solution was passed through one of 38 cation exchange columns contained in two magazines and was collected on a Ta disc and quickly evaporated to dryness.05 M show that the elution position and the width are quite reproducible. the beam energy in the of 330-d target originally consisted of 0. The activity was transported by a He(KCl) gas-jet (2 L/min) over 5 m to the collection site in ARCA II and was collected on polyethylene frits.188 The Chemistry of Superheavy Elements The data for 0. and two new magazines were introduced for the next 114 1-min cycles. 0. Thus.

5. After one hour of irradiation. After evaporation to dryness and flaming. Apart from contamination sputtered from the target (this material is not dissolved by the weekly acidic solution and is washed mechanically through the column). For normalization. the spectrum shown in Figure 15 was obtained. the production rate of the transfer products was determined by height analysis. In these experiments. the Hetransport efficiency was determined. so they are only accurate to 10 or 20%. which passed through the column. The spectrum contains 41 events attributable to element 105. By comparing the apparent on a Pt disc for production rates measured after transport through the He(KCl) gas-jet with the absolute production rates from the Au-catcher experiments. the foil was dissolved in aqua regia to which an aliquot of had been added to trace the chemical yield of actinides. The half-lives of s for 9 pairs of . In 525 collection and elution cycles at 99 MeV. the transport efficiency varied between 40 and 53%. separate bombardments of the Bk target were performed in which all of the products recoiling from the target were caught in a Au-catcher foil located directly behind the target. The actinide fraction. The gold was removed on an anion-exchange column. was collected and dried spectroscopy.05 M and eluting it through an empty column directly onto a Ta disc. among them parent-daughter decays. and from small amounts of Bi and Po activities produced by transfer reactions on a Pb impurity in the target. Liquid-Phase Chemistry 189 experiments by dissolving the activity in 0. the spectrum is very clean. The jet-transport yields are based on the measurement of 50-100 counts.

47]. Also. see Figure 16. The absence of particles above 8. From a chemical point of view. decays with a half-life of and has a SF branch of The cross section of 10±6 nb at 93 MeV is on the same order of magnitude as the 5n cross section at 99 MeV in agreement with evaporation calculations.190 The Chemistry of Superheavy Elements and for were in good agreement with the previously determined values [42]. The procedure was also applied to the products of a ions at the lower bombarding energy of 93 MeV in bombardment with the target in an attempt to discover the unknown isotope produced in the 4n reaction [41]. this means that the data are consistent with a high chemical yield of Db in these separations and with the fact that Db resumes the pentavalent oxydation state under the present conditions [41].5 MeV indicates that the pair is no longer present at the lower bombarding energy in agreement with evaporation calculations.35 and 8. 23 fissions attributable to Db decays were detected. groups at 8.5 MeV. as well as 18 SF events were registered. in the observation of the 8.45 MeV chemically separated Db fractions and by the observation of two events [47] . 9 particles with energies between 8.45 MeV are detected that are assigned to the new isotope and its daughter respectively [41. In a total of 374 experiments. Instead. The mass assignment is supported by the particles of the daughter.3 and 8. These event rates are consistent with the detection efficiency and the known production rate at 99 MeV [42].

were first performed in [50] and and with W isotopes produced with the fission products in the reaction at the PSI Philips Cyclotron. Liquid-Phase Chemistry in which the daughter. As the sorption of Hf on the cationexchange resin was even higher in 0. 4. This would also avoid the formation of mixed chloride-fluoride complexes which are difficult to model.65 and pH = 5 were found to elute W in a one-stage separation from cation-exchange columns and they provided good separations from Hf and Lu. respectively [47]. pH = 2. Seaborgium (Sg. Hf was observed to be partly eluted for M in 0. is a likely form of the complexes that are eluted under such conditions but neutral species such as cannot be excluded.5. Figure 17 shows the elution curve for short-lived tungsten isotopes from the reaction of with enriched . including sometimes the pseudo-homologue U. W.1 M HCl and various HF concentrations between and M were eluting W rapidly while Hf was retained on the cation-exchange resin.1 M M HF. the cross section for production of at 99 MeV as reported earlier [42] had to be revised as it was and the SF branch in and 27-s are produced at this clear now that both isotopes. Element 106) Tests of liquid-phase separations suitable for the group-6 elements Mo. Some problems were encountered with adsorption of the activities on the slider in ARCA II.1 M HC1. Likewise. decay of was followed by the SF decay [48] of the 191 Based on these results. solutions. the decision was made [51] to elute a seaborgium fraction from cation columns using this solution. This shows that chemical separations of transactinides can also be useful in obtaining new data on nuclear properties of their isotopes. and the cross sections for production of and at 99 MeV resulted as 6±3 nb and 2±1 nb. The new value for the SF branch in [47] resulted as 33 %. 34-s energy. titanium showed the lowest losses of W and Hf due to adsorption. Among the various materials tested. solutions with 0.

Figure 18.24% that the three events are random correlations. Three correlated mother-daughter decays were observed that were assigned to the decay of and as the descendants of see Figure 18. Most likely.192 The Chemistry of Superheavy Elements The activity was transported to ARCA II with a He(KCl) gas-jet within about 3 s. On the average. The transport efficiency of the He(KCl) gas-jet was 45%. seaborgium (Sg). Neither divalent or trivalent metal ions nor group-4 ions are eluted within the first 15 s.1 M M HF. see Figure 4.6x8 mm column (filled with the cation-exchange resin Aminex A6. counting of the samples started 38 s after the end of collection.27 random correlations. This gives a probability of 0. . The overall chemical yield for W was 80%. Also the pseudo-homologue uranium. After deposition on a titanium slider it was dissolved and washed through the 1. in the form of is completely retained on the column. the decay of 7-s was not observed because it occurred in the time interval between the end-of-separation and the start-ofmeasurement which is equivalent to four half-lives. 85% of the W elute within 10 s. a flow rate of 1 mL/min with 0. at the GSI UNILAC a 950 target was bombarded with with a half-life of [53]. These three correlations have to be compared with an expectation value of 0. at 121 MeV to produce the isotope 3900 identical separations were conducted with a collection and cycle time of 45 s and a total dose of Ne ions. As the mother decays were not observed. In the experiments [52] with element 106. it is important to note that and can only be observed if passes through the column because group-4 elements and No are strongly retained on the cation exchange columns in ARCA II [35].

With an expected number of random correlations of 0.1 M end. in To this attempts to elute Sg from cation-exchange columns in 0. Thus. a 690 target containing 22 enriched was bombarded with 123 MeV ions [55]. as measured simultaneously for (27% including jet transportation and chemical yield). a total of 5 correlated events was to be expected. 45-s cycles were run in which the effluent from the Aminex A6 columns was evaporated on thin Ti foils mounted on Al frames. Liquid-Phase Chemistry 193 From the observation of the three correlated chains of daughters. Only one pair was observed. i. From the beam integral and the overall yield. there is sorption of seaborgium on the cation-exchange resin. The Ti foils were thin enough to be counted in close geometry by pairs of Si detectors thus increasing the by a factor of four as compared to the efficiency for preceding experiment. see below for results from further investigations. . produced in the reaction served as a yield monitor. in the absence of fluoride ion. The absence of these events is interpreted [55] as to indicate that. A beam dose of ions was collected in attributable to the 4575 separations.5. could not be excluded from these experiments. it could thus be concluded that seaborgium shows a behavior typical of a group-6 element and different from that of the pseudo-group-6 element uranium which is fixed as on the cation-exchange column. . the anionic (“seaborgate” in analogy to molybdate. Presumably. Sg formed or the neutral species but due to the low fluoride concentration used. or tungstate.e.5 this is likely (with a probability of 30%) to be a random correlation. it appeared to be most attractive to test what would happen if no fluoride ions were provided in otherwise identical experiments..

. and Sg [56]. constants of hydrolysis reactions (6-9) were defined [56]. see Section 5. in having a strong tendency to replace this experiment. Equations (6-9). Looking back to the experiments in [52] where fluoride ions were present ligands.194 The Chemistry of Superheavy Elements This obviously non-tungsten like behavior of seaborgium under the given conditions is attributed to its weaker tendency to hydrolyze: The measured equilibrium constants for this stepwise deprotonation scheme for Mo and W have been collected from the literature in [56]. W. it appears plausible that. These results show hydrolysis of the cationic species to the neutral species to decrease in the order Mo>W>Sg which is in agreement with the experimental data on hydrolysis of Mo and W. and on Sg [55] for which the deprotonation sequence may end earlier with a cationic species such as that is sorbed on the cation-exchange resin.V. Pershina and J. They show that Mo is more hydrolyzed than W. relative values of the free energy changes and by use of the hydrolysis model [29. the presence of fluoride ions seems to be an important prerequisite for value of Sg on an anion-exchange resin planned experiments in which the is to be determined with the MCT technique [36.57]. V. Kratz performed fully relativistic density-functional calculations of the electronic structure of the hydrated and hydrolyzed structures for Mo. neutral or anionic species were formed: Thus.30]. and that the deprotonation sequence for Mo and W at pH = 1 reaches the neutral species Assuming the deprotonation processes for the Sg compounds to be similar to those of Mo and W. By use of the electronic density distribution data.

many more interesting chemical investigations in the liquid phase are intelligible. two new approaches .10] would result in a hold-up time too long for 7-s a new apparatus was constructed. Here. Thus. and Mo and W have values on Dowex 1x8 of 82 and 11.1 M M HF. is still present as a cation [35]. forms vs. respectively [36]. distinguished by pulse-shape discrimination PSD and pile-up pulses are rejected by a pile-up rejection system PUR. e. In [57].2. it is in principle capable of investigating short-lived pulses and pulses are nuclides of the transactinides. Thus the feasibility of a Sg experiment with the MCT technique was demonstrated. In 0.57]. measuring Ta. For seaborgium. a slope of –1 in a plot of log was verified indicating that W.. This MCT experiment has been tested successfully with shortlived W isotopes and awaits its application to Since the fast centrifuge system SISAK is equipped with liquid scintillation counting LSC [12. Mo. an solutions containing HCl.1 M M HF and is fed into the 3-column system quasi continuously. anion separation scheme in mixed solutions was elaborated for a W/Ta separation on an anion-exchange resin with the quaternary ammonium group for which relatively low values for W and high values for Ta are observed yielding a W/Ta separation factor of 2270. in the presence of HF. it is planned to determine the value on an anionexchange resin (Dowex 1x8) in 0. Liquid-Phase Chemistry 5. By varying the concentration of the counter ion consistent competing for the binding sites on the resin.e. With this resin. are As the daughters of and cations in solutions at sufficiently low HF concentrations. batch and MCT experiments were performed yielding mutually values. A large amount of work has been invested to prepare this important experiment by values in batch experiments for tracer activities of Zr. the activity-bearing aerosol is deposited for 2 s on a Ta disc by impaction Thereafter. This analog electronics proved to result in insufficient background suppression.1 M M HF. i. log anions with an electric charge of –1..5. a separation scheme for the planned Sg experiment is to use cation-exchange while the resins for the filter column F and the daughter column chromatographic column C contains the anion-exchange resin Dowex 1x8. Th with various resins of different functionality and aqueous HCl/HF.g. Hf. and [36.58]. the Ta disc with the active spot is rotated into a position where the activity is dissolved within 2 s in 0. W. Perspectives 195 For rutherfordium and for dubnium. As a continuous dissolution of the KCl aerosol of the transport jet in a degassing unit of the type used in [9.

196 The Chemistry of Superheavy Elements are being pursued: K. 114. [59] have coupled the existing PSD/PUR electronics with a fast transient recorder which records the LSC pulses in 500 2-ns steps thus facilitating the recognition of background pulses in the off-line analysis. These digitally recorded pulses will be subject of analysis by a neural network that has been trained with events. a combination of both i) digitally recording of LSC pulses plus their analysis by a neural network and ii) reducing the amount of reaction products entering the SISAK system with a pre-separator gives the most promising perspective. Omtvedt et al. a potential is calculated that characterizes the process at 50% deposition: . and 116 [63-66] confirming the over 30 years old theoretical prediction of an “island of stability” of spherical superheavy elements. pile-up events in order to recognize true events [60]. In addition. This is reproduced in a macroscopic model [70].69]. in which the interaction between the microcomponent A and the electrode material B is described by the partial molar adsorption enthalpy and adsorption entropy. The chemistry of these elements should be extremely interesting due to the predicted dramatic influence of relativistic effects [67]. has recently announced the observation of relatively long-lived isotopes of elements 108. It is known that the potential associated with the electrochemical deposition of radionuclides in metallic form from solutions of extremely small concentration is strongly influenced by the electrode material. events. An example is the separation procedure proposed for liquid-phase studies of element 107. the chemical identification of the newly discovered superheavy elements is highly desirable as the observed decay chains [63-66] cannot be linked to known nuclides which has been heavily criticized [68. Russia. Eberhardt et al. Thus it is obvious that their electrochemical deposition could be an attractive method for their separation from aqueous solutions. J. [61] performed recently first successful experiments with by coupling SISAK to the Berkeley Gas Filled Separator (BGS). Elements 108 – 116 are homologues of Os through Po and are expected to be partially very noble metals. Due to the half-lives of the observed isotopes in the range of seconds to minutes. 112. Probably. By combination with the thermodynamic description of the electrode process. and Another perspective for SISAK is to suppress the interfering background by an electromagnetic separator. The Flerov Laboratory of Nuclear Reactions (FLNR) in Dubna. 110. chemical investigations of these heaviest elements in the Periodic Table appear now to be feasible. bohrium (Bh) [62].P. see Chapter 4 for more details. Various liquid-liquid extraction schemes for the transactinides have already been elaborated.

and the surface of 1 mol of A as a mono layer on the electrode metal B [70]. Cu-. and Po. particularly large. n is the number of electrons involved in the electrode process. Liquid-Phase Chemistry 197 Here. The perspective is to make use of the Pd or Pt in form of a tape on which the tracer activities are electrodeposited and the deposition zone is subsequently stepped between and SF measurements. Ag-. The latter are metals in which. a number of models were used in [70] and calculations were performed for Ni-. An application of the same model to the superheavy elements still needs to be done. and Au-electrodes and the micro components Hg. is the partial molar net adsorption enthalpy associated with the transformation of 1 mol of the pure metal A in its standard state into the state of “zero coverage” on the surface of the electrode material B. For the calculation of the thermodynamic functions in (12). For Pd and Pt. Bi. is the difference in the vibrational entropies in the above states. larger than the standard electrode potentials tabulated for these elements. due to the formation of the metallic bond. This makes these electrode materials the prime choice for practical applications. such that these metals tend in an extreme way towards the formation of intermetallic compounds with sp-metals. Tl. F the Faraday constant. Pt-. Pb. pairs of Si detectors for . Pd-. positive values of were calculated.5. but one can anticipate that the preference for Pd and Pt will persist. almost or completely filled d orbitals are broken up. confirming the decisive influence of the choice of the electrode material on the deposition potential.

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. Hofmann.V. Gorschkov.P. Alstad.G. J.Sh.. S...A..G. G. A. V. Nitsche. H. 50. Karelin. Chepigin.. Nähler..N. Liquid-Phase Chemistry 201 61... A 7. In: Encyclopedia of Computational Chemistry. von R.. B.M. G.. O. G.M. R.N..L. S. R. D. Kirbach. Subbotin. Buklanov.V. Yu.I.: Phys.. R.. A. J... Omtvedt.Ts. Schreiner. (1999) 242..W. G. Sci.. A. Itkis. M.. A.F. Alstad. Utyonkov..... A. Malyshev..V.. Johansson. 63. Gigkal....P.. Lobanov..M... 68. M.. Stoyer.N.. K. (2000) 04160. Radioanal. 70. (2000) 475.. Sagaidak. Saro. A 5.. A.. N. Seth. Rev..A..Sh.V. Subotin. Nucl.L. O. 66. N.L. Schwerdtfeger. V. Tsyganov. Malmbeck. R.A. Yu. Rev. Morita. A.G... J.. A.: J.. Veselsky. Popeko. 246. A. P. (2000) 411. Eichler.. K. Stavsetra.G.L. Morita. Armbruster. G.G. L. Nucl.. K. Ivanov.. Buklanov. Rohac.J. Bogomolov. Itkis. Stoyer.. Yeremin.P.P. S.L. Chepigin.G. .. V. 65.. Sudowe.. Itkis. Gulbekian. V. Moody. F. (2000) 23.: “Relativistic Effects of the Superheavy Elements”. M. S. Gulbekian.. G. Zielinski. S. Omtvedt.. Yeremin...: Radiochim. D.M.. P.R. Kabachenko. Bogomolov. J. U. K. Gikal.N. N.. N. Iliev.. G.5. Hayama.A.. J. Giardina.N. Chelnokov. Rohac...A. R. Wild.: Structure and Bonding 21. Vol. Bogomolov. T.. Phys. M.: Annu. M.N. Ye. M.V. Laue. H. A.: Eur.N. Yu. S.N. V.. Itkis...N. J.K. F. Mendel... Tatarinov. Schleyer..G. R..K. Isyganov.V. Bogomolov... P. P. A. Yu... Lavrentev..V.Ts. 71. J. O. G. V. Münzenberg.. Japan. Lavrentev. C 62. M. Rev.G. Allinger.. J. B. 67. M.. Polyakov. Kollman.I. Popeko.C. Saro. S.. P.. Part.. Yu.. B.. M. S. (1975) 89. Y.. V.N.: Abstract submitted to Actinides 2001. J.N.B. N. Gulbekian. A.A. Abdullin. Iwasa. G.G... Polyakov... (2000) 349. V. Stoyer... (2001) 011301..S. S.N..G.. I.J. Lougheed. Oganessian. Lee. Schaefer III. Hoffman.. B.. C. M. Stoyer.. (1999) 63.. A. Gasteiger. Shirokovsky. Gorschkov. Malyshev. Ivanov. G.Ts.W. Iliev. 4.J. Skarnemark. Oganessian. J. S. 64 Oganessian.Yu. Johansson. New York.Ts. A..V. 69.F. Folden.V... Trautmann. Kabachenko. 62. Shirokovsky. Sukhov.. Subotic.: Phys. (1998) 2480.: Eur. K. O. Skarnemark.. A. Kutner. Wiley. Moody. Patin.. Mezentsev. Yu. Chem. Subbotin. Wiehl. Clark..Yu.L. Sgaidak.. V. Oganessian. Gikal. Hofmann. M.. K. Buklanov. Lobanov. J. Fricke. Yu. J. P. B. C 63...V..W. Kratz.. Wild. Armbruster.A. Fure. Phys..F.J. J.V. K. Lougheed.. G. Acta 88. Mezentsev. Eds.: Nature 400. M. N. Sukhov.V..N. Gikal.. I. S.B. K. R.. Yu. Eberhardt. C.. Abdullin. Gulbekian..G.. B.G. Utyonkov.

175. 181. 167. 196 Mainz TRIGA reactor 187 Maximum likelihood 177 MCT 160. 189. 195 Cross section 175. 187 Hydrolysis 162. 169. 184. 169. 192 Group-5 elements 167. 170. 167. 193 Batch experiments 168. 166. 173. 194 Impaction 164. 183 Cobalt ferrocyanide 165 Coordination number CN 165 Counter ion 169. 168. 186. 195 Liquid-liquid extraction 159. 182. 177 183.202 The Chemistry of Superheavy Elements Index Dubna U-400 Cyclotron mother-daughter correlations 161 162. 174. 185. 191. 185. 166. 184. 165. 175. 167. 183. 166. 164. 193. 181. 190 Deprotonation scheme DIBC DS DV method 170 Electrochemical deposition 196 167. 175. 170. 170. 184. 171. 171. 172. 187. 182. 186. 195 value 159. 171. 174. 182. 178. 193 Cation-exchange resin 160. 171. 183. 178 Mother-daughter correlations 177 Neural network 194 182 167 196 . 174. 166. 171. 192. Sg) 192 Element 107 (bohrium. 171. 191. 179. 175. 195 MIBK 177. 175. 168. 196 160 Adsorption experiments 175. Cation-exchange column 170. 172. 184 Breakthrough volume 169 Cation-exchange chromatography 160 169. 192. 170. 177. 194. 187 He(KF) gas jet 185 HPLC 178. ARCA II 174. 195 Beam intensity 174 Berkeley 88Inch Cyclotron 163. 191. 179. 191 decay events 175. 186 Aliquat336 Anion exchange resin 174 Anion-exchange chromatography 159 Anion-exchange columns 172 160. 194. 183. 162. 170. 173. 194 Chloride complexes 162. 165. Db) 175 Element 106 (seaborgium. 177. 181. 185. 169. 186 Group-6 elements 191 He(KCl) gas jet 171. 171. 191 Group-4 elements 162. Rf) 160 Element 105 (dubnium. Bh) 196 196 Fast transient recorder Fluoride complexes 166. 194 Electronic structure Element 104 (rutherfordium. 174. 182. 188.

166 TBP 164. 166. 170. 191 Si(Au) surface barrier detectors 175. 169. 171. 179 Separation factor 195 SF decay 179. Liquid-phase Chemistry 203 Philips Cyclotron 166. 187 . 179. 169. 171. 191. 181. 177. 186. 195. 178 SISAK 160. 180. TiOA 182 Transactinides 160.5. 197 Superheavy elements 164. 187 Volume 160. 196 171 Specific activity 196. 195. 191 Pile-up rejection 195 PIPS detector 164 Pulse-shape discrimination 195 Retention time 159. 196 Trioctyl-methylammonium chloride 162 TTA 164 UNILAC accelerator 171. 168 Reversed-phase extraction chromatography 159. 168.

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Germany Part I: Basic principles of the determination of adsorption properties using gas-phase adsorption chromatographic methods 1. available for gas adsorption chromatography. 205 M. are well established methods in nuclear chemistry. Eichlerb a Paul Scherrer Institut.Chapter 6 Gas-Phase Adsorption Chromatographic Determination of Thermochemical Data and Empirical Methods for their Estimation B. different stationary phase materials. In addition. see Table 1. Printed in the Netherlands. Schädel (ed. Formation probabilities of defined chemical compounds and their volatility can be investigated on the basis of experimentally determined and of predicted thermochemical data. are further broadening the areas of application. R. combined with gas adsorption chromatographic investigations. Volatile elements as well as a large variety of volatile chemical compounds can be investigated by using a broad assortment of reactive carrier gases. Switzerland b Gesellschaft für Schwerionenforschung. the latter are discussed in Part II of this chapter. Eichlera. The Chemistry of Superheavy Elements. D-64291 Darmstadt. . Moreover. © 2003 Kluwer Academic Publishers. Introduction Volatilization processes. Fast reactions and high transport and separation velocities are crucial advantages of these methods. 1.). 205-236. Planckstr. the fast sample preparation for and spontaneous fission measurements directly after the gas-phase separation is a very advantageous feature. CH-5232 Villigen PSI.

applied to the column. which were obtained applying the described evaluation methods in gas-adsorption chromatography. as the flow rate and the type of carrier gases. Practically. As the quantities of elements applied in nuclear chemistry are often small. For results. or to characterize the absorbate from its experimentally observed behavior in a process. e. the separation quality can be influenced by the size of the chromatographic surface. While Part I of this chapter is devoted to basic principles of the process.g. see Chapters 4 and 7 of this book. and the interaction of the gaseous atoms and molecules with the column surface (the stationary phase). the derivation of thermochemical data is discussed in Part II. the design of the chromatography columns. Suitable chemical states and stationary phases exist for almost all elements to allow their investigation in adsorption chromatography. respectively.. The volatilization and the gas phase transport through a chromatography column depend on experimental parameters. the temperature. Symbols used in the following sections of Part I are described in Section 5. Experimental investigations were carried out in the temperature range from 2400 K [1] to 85 K [2]. down to one-atom-at-a-time. deposition and volatilization are predominately related to adsorption and desorption phenomena. by fillings in the chromatography column. . in order to design experiments.206 The Chemistry of Superheavy Elements Apart from that. which are related to the adsorption-desorption equilibrium. pure condensed phases do not occur. These methods can either be used to predict the behavior of the adsorbates in the chromatographic processes. This chapter describes basic physico-chemical relations between the gas phase transport of atoms and molecules and their thermochemical properties. The entire gas phase transport is called gas-adsorption chromatography.

Equations 52-54).6. Section 2. It is defined according to its expediency. regardless of the possibility of its physical realization. The standard state is freely selec­ table. the solid and the gas phase: Here we consider the simple adsorption-desorption reaction equilibrium of a reversible mobile adsorption process without any chemical reactions: For the formulation of a dimensionless adsorption equilibrium constant the definition of a standard state is crucial. The standard state of adsorption is assumed to be the ratio of a standard molar volume to the standard molar surface [4]. Thermochemical Description of the Transport of Substances in Gas-adsorption Chromatography Processes 207 2. In addition. The reaction enthalpy and entropy has to be introduced into the calculations [5-8] as well as the .1 THE ADSORPTION EQUILIBRIUM This description is based on the differential equation for the transport velocity of a substance in the ideal linear gas chromatography [3]: represents the partition coefficient corrected by the ratio of both phases. Empirical Models in Gas-Phase Adsorption Chromatography 2.3. The dimensionless equilibrium constant of a simple reversible adsorption reaction is related to thermodynamic standard quantities – the standard adsorption enthalpy and the standard entropy of adsorption which are assumed to be temperature independent: For a localized adsorption the concentration of the adsorption sites has to be taken into account [4]. e. dissociative and substitutive adsorptions as described in Part II of this chapter (Part II.g. a reversible change of the chemical state of the adsorbate in the chromatography process has to be considered.

for short-lived nuclides. at the temperature. the temperature dependency of the carrier gas flow rate. from the standard entropy of solid metals.208 The Chemistry of Superheavy Elements equilibrium constant for the chemical reaction with its standard states of the occurring chemical states of: The entropy of a mobile adsorption process can be determined from the model given in [4]. The phonon frequency can be evaluated from phonon spectra. where 50 % of the nuclides pass the isothermal chromatography column. is transferred into the adsorbed state with two translational degrees of freedom parallel to the surface and one vibration degree of freedom vertical to the surface.2 ISOTHERMAL GAS CHROMATOGRAPHY Combining Equations 1-5. It is based on the assumption that during the adsorption process a species in the gas phase. Thus the retention volume is calculated as: In experiments with long-lived nuclides retention times equal the time of the experimental duration. that the adsorbed species are vibrating in resonance with the lattice phonon vibrations of the solid stationary phase. From statistical thermodynamics the following equation for the calculation of the adsorption entropy is derived: As a good approximation it is assumed. the retention time equals the half-life of the species: . where it has three degrees of freedom (translation). and integrating over the column length the following relation for the retention time in isothermal gas chromatography is obtained [10]: The first addend in Equation 10 can be neglected. from the Debye temperatures or from the Lindemann equation [9]. However. 2.

For x »1 this function can be estimated by: For which is mostly the case. the first addend in Equation 15 is negligible and .6.3. The temperature profile along the chromatography column is approximated to be linear by: The substitution of the corrected partition coefficient and the introduction of the standard state (eq.3 THERMOCHROMATOGRAPHY 2.1 Gas thermochromatography The given description of the gas phase transport in a tube with a temperature gradient is only valid for adsorption equilibria of reversible mobile adsorptions without any superimposed chemical reaction.1-8) lead to: the integration yields: Ei*(x) is the exponential integral function of x. 2. Empirical Models in Gas-Phase Adsorption Chromatography 209 can be evaluated from the slope of an Arrhenius-type plot of the From the retention volume (first term in Equation 11) against intersection with the ordinate axis can be evaluated.

At molecular flow conditions the linear velocity of the carrier gas. According to a limited experiment duration and radioactive life-time of the species this leads to a deposition zone of the adsorbate in the column. that Equations 17 and 20 are only valid. on the thermochemical constants of the adsorption reaction. 2.2 Vacuum thermochromatography The model of ideal linear gas chromatography (Equation 1) [12] also describes the transport of a chemical species in the temperature gradient of a vacuum tube. .210 The Chemistry of Superheavy Elements Hence.3. The retention time for a short-lived radioactive species is calculated as the radioactive lifetime of the nuclide: or equals the duration of the experiment for a long-lived species. the following simplification [11] is conceivable: Thus. This from the end of the length is the distance of the deposition region with Thus. The simplification of Equation 17 is not possible. which is identical to the transport velocity of the adsorbate in the gas phase. Note. if very short-lived nuclides are used. the deposition temperature and the thermodynamic state function of the adsorption are combined and they can easily be determined from each other. if the chemical state of the investigated species does not change along the entire temperature range. is assumed to be similar to a corresponding effective length of the column at which this species would have exited. has to be substituted by the fraction of the column length over the average retention time of the species in the column: The deposition site of a species in a defined temperature region. the average retention time is a function of the column column with volume and of the conductivity of the column for inert gas phase species at molecular flow conditions. under conditions where the retention time in the adsorbed state exceeds the duration of the experiment. The probability of residence of the species in the adsorbed state is mainly dependent on the temperature dependent equilibrium constant and thus. An increasing adsorption probability with lowering temperatures leads to a decrease of the migration velocity of the adsorbate zone.

and is obtained: For practical applications some simplifications [13] similar to Equations 18 and 19 lead to: Hence. For experiments with very short-lived nuclides the Equations 12. Empirical Models in Gas-Phase Adsorption Chromatography 211 Applying Equation 1 and substituting the corrected partition coefficient by a gas phase kinetic formulation of the adsorption equilibrium constant the following functional dependency between the retention time. temperature Again this simplification holds only for [14. again. . Introducing the mobile adsorption model into this derivation [16] to: changes Then Equation 12. 22. and 28 have to be combined and.15]. 13. 22. and 23 have to be combined and the resulting integral has to be solved numerically. the resulting integral has to be solved numerically. the experimental parameters. from the experimental parameters and from the measured deposition can be determined.6. 13.

To determine of the adsorbate on the stationary phase the experimental parameters and the physical data of the carrier gases and of the adsorbate are used as an input into these models. of a gas-phase adsorption process for radioactive species are: 1. These models open the way for a microscopic description of the chromatographic adsorption-desorption process on an atomic scale. see Chapters 4 and 7. The Chemistry of Superheavy Elements Microscopic Kinetic Description of the Adsorption Process in Gas Chromatography . For a set of values the model yields chromatograms which are compared to an actual value is obtained from the best agreement experimental result. The formalism can easily be adapted to a PC-based program for an from gas adsorption chromatographic results and. they are kinetic models of gas adsorption chromatography. The Monte-Carlo principle uses random numbers in the region The main randomized values in the Monte-Carlo simulation. which are successfully applied for the evaluation of adsorption enthalpies in gas-phase adsorption chromatography investigations of the heaviest elements and their lighter homologues. to predict the behavior of an adsorbate in gas chromatography from its known adsorption data. For their derivations see [17]. Hence. which is distributed logarithmically of the nuclide according to the radioactive decay law with the half-life. The formulas used in the PC-based simulation are given here. For every atom a random lifetime.212 3. is calculated: . A flow chart of the Monte Carlo model is presented in Figure 1. The application of Monte-Carlo simulation methods in gas adsorption chromatography is based on ideas given in [17].1 GAS CHROMATOGRAPHY WITH CARRIER GASES This section explains the basic principles of Monte-Carlo models. evaluation of the vice versa.Monte Carlo Methods 3. see Figure 1. The radioactive lifetime. The between model and experiment.

Empirical Models in Gas-Phase Adsorption Chromatography 213 .6.

which is distributed logarithmically. can be calculated: . The mean number of wall collisions along is The randomized number of wall collisions during the travel of the atom is distributed logarithmically: The mean residence time of the atom in the adsorbed state is calculated by a Frenkel-type equation: Hence the residence time of the atom in the adsorbed state. which is distributed logarithmically too. The residence time. The mean jump length of the adsorbate can be approximated by: The pressure and temperature dependent diffusion coefficient of the adsorbate in the carrier gas is approximated according to Gilliland [18]: The gas flow also depends on the temperature and on the pressure. The jump length and the time of flight in the gas phase. the time the atom remains in the gas phase can be derived: 3. is calculated by: Thus. the random jump length. Assuming an ideal gas behavior of the carrier gas it can be calculated from the flow rate at standard conditions: Subsequently.214 The Chemistry of Superheavy Elements 2.

The solid angles of desorption from a plane surface into the vacuum are calculated according to Knudsen [19] assuming a cosine law: For the cylindrical column this approach leads to the following picture: The velocity of the atoms can be set as the arithmetic mean velocity from the Maxwell-Boltzmann distribution. Empirical Models in Gas-Phase Adsorption Chromatography 3. can be calculated: The transport of species along the chromatography column is assumed to be dependent only on the solid angle of the desorption direction and on the dimensions of the column.2 GAS CHROMATOGRAPHY IN VACUUM 215 A Monte-Carlo simulation of gas chromatography at vacuum conditions follows the same scheme as of Figure 1 [16]. The lifetime of each atom or molecule is calculated using Equation 28.6. which is distributed logarithmically. The mean residence time of the atom in the adsorbed state at a defined temperature is calculated using Equation 34. the time the atom is in flight can be calculated as: The column is assumed to be “closed” at both ends. The residence time of the atom in the adsorbed state. It only dependents on the temperature and their molecular weight: Hence. .

216 4. column fillings) can be evaluated. The surface geometry has to be simple. Summary The Chemistry of Superheavy Elements At this point we would like to state some advantages and disadvantages of the thermodynamic and the kinetic approach. The probability that the adsorbate is transported along the column by “long jumps” is taken into account. . Advantages of the thermodynamic model: It is less time consuming. Advantages of the kinetic Monte-Carlo model: The description of the microscopic chromatographic process at realistic temperature conditions at the surfaces (real temperature gradient) is possible. which is important to describe the chromatographic separation especially at high gas flow rates. The radioactive decay is approximated through an average lifetime. where complex stationary phases have been used (e. Disadvantages of the kinetic Monte-Carlo model: The evaluation is time consuming.g. Disadvantages of the thermodynamic model: The a linear temperature gradient has to be assumed. Experiments. “Long jumps” cannot be described in the model of linear gas chromatography. The probability distribution of the radioactive decay of the adsorbate is included.

D h K k L m N p random R s standard gas concentration of the adsorbate. free open cross section area of the column. dimensionless reaction equilibrium constant. 8. J/mol equilibrium constantof adsorption.31441 J/mol·K open surface of the column per 1 m column length. 1/s pressure. J/K length of the column. density carrier gas at its melting point. standard surface concentration of gas concentration of the adsorbate. . 101325 Pa random number gas constant. Empirical Models in Gas-Phase Adsorption Chromatography 5. m partition coefficient corrected by the phases.6. kg molar weight adsorbate. Planck's constant. the adsorbate. (ideal gas at STP) density of the adsorbate at its melting point. kg/mol molar weight carrier gas. dimensionless Boltzmann constant. Pa standard pressure. m atomic or molecular mass of the adsorbate. kg/mol number of atoms number of wall collisions mean number of wall collisions maximum lattice phonon vibration frequency. J·s free standard adsorption enthalpy of adsorption. m diffusion coefficient of the adsorbate in the carrier gas. K/m surface concentration of the adsorbate. negative temperature gradient. Symbols 217 A a inner surface per 1m column length. J/mol free standard adsorption enthalpy with chemical reaction. dimensionless distribution constant. J/mol standard enthalpy of reaction. J/mol standard adsorption enthalpy at zero surface coverage. inner diameter of the column.

K standard temperature. s lifetime.218 The Chemistry of Superheavy Elements standard entropy of adsorption at zero surface coverage. K deposition temperature. s upper (start) temperature of the gradient. coordinate longitudinal to the column. 298. carrier gas flow at STP. s temperature. s transport time. m mean jump length. s retention time. m/s carrier gas velocity at STP. J/mol·K time. m t T u V v y . s mean time the adsorbate keeps adsorbed. K carrier gas velocity. m/s inner volume of the column. m path length. carrier gas flow. s duration of the experiment. open volume of the column per 1 m column length. s time the adsorbate keeps adsorbed. m jump length.15 K half-life. K isothermal temperature.

atomic and ionic radii as well as binding energies in isolated single gaseous molecules of defined chemical compounds with satisfactory accuracy.6. "Empirical" and "exact" methods are both of high importance for the prediction of properties of transactinide elements.stimulated the work on theoretical predictions of their chemical properties. Due to the extremely low production rates of transactinides in the nuclear fusion reactions. the predictions of these properties are instrumental for the design of experiments and indispensable for the interpretation of experimental results. Our intention is to present empirical methods [20-35]. in the gas adsorption chromatographic process. The stability and the volatility are chemical properties. which is necessary for the evaluation of the volatility of compounds. They provide a fast separation of transactinides from a wide variety of by-products. the chemical characterizations are carried out on a single atom level. ionization potentials. the accuracy of the methods is not sufficient. Gas chemical methods are successfully applied for the chemical characterization of transactinides. These methods are mainly based on the measurement of adsorption properties of the atomic or molecular state of transactinides on different stationary phases. It is in principle impossible to calculate the behavior of a single atom or molecule in an experimental setup "exactly". In this process the formation probability of defined chemical states of transactinides and the subsequent interaction of the formed molecules with a solid state surface are studied.the transactinides or superheavy elements . The chemical reaction products are characterized on the basis of their behavior in the separation process or. which define the behavior of the transactinide element or its compound in the gas adsorption chromatographic process. yield the atomic ground state configuration. which are described in Chapter 2 of this book. The "exact" ab-initio methods. Therefore. Introduction The discovery of new chemical elements . exactly speaking. . which can be used to predict chemical properties and which are relevant to gas phase chemical studies of transactinides. which are instantly produced in the nuclear formation reactions of transactinides. Empirical Models in Gas-Phase Adsorption Chromatography 219 Part II: Derivation of thermochemical data with respect to the periodicity of properties and their interrelations 1. For the ab-initio calculation of the stability of pure solid phases.

The calculation of the volatility of the elements and of their compounds. The main steps in this process are: I.).220 The Chemistry of Superheavy Elements Up to now. II. and V. VIII. Steps VII and VIII are discussed in Chapter 4 and 7. VII. and the periodicity of chemical properties and trends along the groups of the periodic table. respectively. More details concerning step V and step VI are outlined in Chapter 2 and 4. III. . the confirmation of predictions of the chemical reaction behavior and of the volatility. the relative volatility of equivalent chemical compounds compared with the homologues.. Design of an experimental set-up for experiments with transactinides with respect to the predicted adsorption properties and its half-life using III. The prediction of the adsorption behavior of transactinides or their compounds at zero surface coverage from the predicted volatility (II. retention times and decontamination. VI. The contribution to this chapter focuses on the steps I-IV. the adsorption enthalpies and the volatilities of fictive macroscopic phases. Model experiments using short-lived nuclides of lighter homologues for the determination of reaction rates. IV. The interpretation of the results according to: the formation of compounds with similar volatility as known from their homologues. V.) applying the empirical correlations (III. only empirical methods can predict the volatility of compounds. The analysis of thermochemical data of chemical compounds in the solid and in the gaseous phase. The physico-chemical description of the gas adsorption chromatographic process. These predictions represent an important part in the multiple step process of the chemical characterization of transactinide elements. The experimental determination of empirical correlations between the volatility of the pure macroscopic phase and the adsorption behavior of single atoms or molecules on defined surfaces.

and the sub-shell closure of the p-. d-. Trends of chemical properties of the elements and their compounds exist in the groups of the periodic table. and which lead to discontinuous variations of properties along the groups. assuming that all transactinides systematically belong to defined groups rough estimates about their chemical properties are feasible.33-38]. have to be considered [36-38]. Therefore. which do not exhibit such effects. elements with a shell closure or a half-filled electron shell in their ground state configuration form relatively volatile condensed phases and less stable chemical compounds compared to elements in the same group. which depend on the atomic number. Empirical Models in Gas-Phase Adsorption Chromatography 2. the resulting information on the volatility of the investigated chemical species is as reliable as results from experiments with a very large number of atoms or molecules from one evaporation-deposition experiment. In general.6. For these estimates shell effects and relativistic effects.28. Therefore. These values are always relative stability measures in combination with a competing chemical state. Thermochemical Data 221 2. no direct functional dependence exists between thermochemical state functions and electron configurations. Thermochemical state functions normally describe the behavior of a large number of atoms or molecules.1 EXTRAPOLATIVE DEDUCTION AND ANALYSIS OF THERMO­ CHEMICAL DATA FOR TRANSACTINIDES AND THEIR COMPOUNDS It is assumed that the stability of a chemical state can be expressed in terms of the standard formation enthalpies of gaseous and solid compounds and of their atomic standard formation enthalpies Both values differ only in the elemental state: The first value stands for the standard state of the element and the second one for the gaseous monatomic state of the elements at standard conditions.due to relativistic effects [21. For the description of single atoms we use these values as a measure of the formation probability of different chemical states and to quantify the binding energy in molecules. during which a single atom or molecule changes its chemical state in thousands of adsorption-desorption steps. which act especially on the chemical properties of elements with lower atomic numbers. This creates a dilemma for extrapolative predictions of thermochemical data of transactinides along their groups as these configurations change with atomic or row number. . Examples for such effects are: the half occupancy of electron shells.the transactinides . For more detailed information on this topic see Chapter 3 of this book. Anyhow. and felectron levels with an increasingly strong spin-orbit splitting for elements at the highest row numbers .25. Gas-adsorption chromatography is a multi-step process.

They are used as primary input values for extrapolative predictions and they are mostly equal to the standard sublimation enthalpy of these elements. This value is a substantial constituent of the binding enthalpy of compounds [41]. Therefore. They can be estimated empirically for the transactinides by considering shell effects in the region of their homologues and by extrapolations along the groups and along the rows of the periodic table (Method 1) [28].40]. In an illustrative way.elements are presented in Figure 3. data for s.. a coupling between the standard or the atomic standard formation enthalpies of solid and gaseous compounds and the standard enthalpy of monatomic gaseous elements can be expected and is certainly observed. e.222 The Chemistry of Superheavy Elements In the following part methods are outlined.g. In this case electron shell effects in the homologues are already implemented. which can be used to master the described dilemma. the standard enthalpies of monatomic gaseous elements are of fundamental importance. To estimate standard formation data of transactinide compounds in their solid and in their gaseous p. . see Figure 4. More trustworthy extrapolative predictions are possible by correlating thermochemical state functions mutually. As an example. the standard enthalpy of monatomic gaseous elements can be seen as the dissociation enthalpy of a (macromolecular) elemental crystal [39.

Recently. Empirical Models in Gas-Phase Adsorption Chromatography 223 The enthalpies of formation obtained by this extrapolative Method 2 are listed in Table 2. More generally. this type of correlation is observed for different compounds of transition elements in their highest achievable oxidation state. correlations between the standard formation enthalpies or the atomic standard formation enthalpies of the solid state versus the corresponding values of the gaseous state have been used (Method 3) [42. .43]. For similar types of compounds of elements along one group with equivalent oxidation states linear correlations can be observed. Two results are given for the formation enthalpies. wherever different values of the standard enthalpies of monatomic gaseous elements are predicted.6. see Figure 5.

224 The Chemistry of Superheavy Elements .

. the formation enthalpy of a compound in its solid or gaseous state can be predicted (Method 4). their standard entropy of the pure solid phase. Thus. just by assuming the oxidation state of a compound. Empirical Models in Gas-Phase Adsorption Chromatography 225 Interesting linear relations were obtained by Golutvin [48] correlating the standard formation enthalpies of solid and gaseous compounds of elements see Equation 44). The individual crystal lattices with their characteristic binding properties and thus. For the adsorbed state the relevant quantity is the desorption pressure. which depends on the temperature and on the surface coverage. 2.2 VOLATILITY The temperature dependent vapor pressure of pure elements or compounds is frequently used to define volatility. see Figure 6. which are normalized to the oxidation state of the metal ion in this compounds (w) and to the number of metal ions (metal with the logarithm of the oxidation equivalents) in the compounds state of the metal ion in this compounds.6.

e. especially for the halides.226 The Chemistry of Superheavy Elements may largely influence the vapor pressure [42]. . However. and 7 are included in Table 2. The prediction of the adsorption behavior of a transactinide compound starts of the pure with the calculation of the sublimation enthalpy compound..g. the standard sublimation enthalpy can be calculated using the following methods: Method 5: Calculations employing the difference between the standard formation enthalpies of compounds in the gaseous and in the solid state: Method 6: Correlations between the standard formation enthalpies of the gaseous and of the solid state with the linear regression coefficients a and b. in this procedure it is important to use consistent sets of radii for all homologues. Thus. we define the standard sublimation enthalpy as a measure for the volatility of a compound. Sublimation enthalpies derived from Method 5. Depending on the availability of data.g. see e. Figure 7. see Figure 4: The standard sublimation enthalpy is then calculated by: Method 7: Significant correlations exist between ionic radii in the solid state -or radii of electron orbitals of ions -and the sublimation enthalpies for various compound classes. It is possible to calcu­ late the standard sublimation enthalpy of transactinide compounds from their calculated ionic radii by making use of a radii-volatility correlation and of corresponding radii of the homologues [44]. 6.

: The experimental proof of such correlations for defined classes of pure substances is essentially for the prediction of adsorption properties of transactinides and their compounds. Hence. which undergo diffusion processes or irreversible reactions with the stationary phase. The selection of proper elements and compounds needs to take into account the very complex situation. In the adsorbed state at zero surface coverage the individual variations of the entropy are partly but not completely suppressed. which are unstable under the selected conditions. In principle all compounds. see also Figure 8 A-C: For elements (with [50] for chlorides and oxychlorides (with [42] and for oxides and oxyhydroxides (with [51] The results of these empirical correlations clearly prove the postulated proportionality. a variety of gas adsorption chromatographic experiments were carried out with carrier free amounts of different radioisotopes using selected modified surfaces as stationary phases. which characterizes the volatility properties of pure solid phases as an integral value. The following correlations (Method 8) were obtained experimentally for elements and selected compound classes. it is expected that this adsorption enthalpy is proportional to the standard sublimation enthalpy.3 EMPIRICAL CORRELATIONS BETWEEN ADSORPTION PRO­ PERTIES OF SINGLE ATOMS OR MOLECULES AND THE VOLATILITY OF PURE SUBSTANCES Empirical extrapolative predictions regarding the stability and the volatility of transactinides and of their compounds are. Therefore. The chemical state of the radioisotopes in the reactive carrier gas and the standard sublimation enthalpy of this chemical state must be known. Empirical Models in Gas-Phase Adsorption Chromatography 227 2. The use of carrier free amounts is necessary to experimentally obtain adsorption conditions at nearly zero surface coverage.6. respectively. These correlations suggest a similarity between the bond . It is assumed that the binding energy of an adsorbed single molecule to the surface approximately equals its partial molar adsorption enthalpy at zero surface coverage. in the next step. have been rejected as well as compounds. followed by the determination of empirical correlations between adsorption properties of extremely small amounts of these elements or compounds and the volatility of the pure macroscopic solid phase of this substance.

These results are only valid for experimental conditions using the same reactive gases and thus. an adsorption and desorption of molecules without any change in the oxidation state and no change in the ligands. respectively. especially at high temperatures.52-57]. in the case of dissociation reactions. Adsorption processes of molecules with non saturated coordinations show much stronger interactions. Pure and very reactive gas mixtures are used at high concentrations to obtain this chemical state. oxidation state and number of ligands. The adsorption behavior of atoms and compounds for most of the experiments used in the described correlations were evaluated using differently defined standard adsorption entropies [28. which is relevant for the desublimation process. Two fundamentally different types of reversible processes can occur in the gas adsorption chromatography [7]: (i) Firstly. in some cases. In addition. During gas adsorption processes the reactive carrier gas determines the chemical state of the investigated elements and modifies the surface of the stationary chromatographic phase in a characteristic way. the simple adsorption of a group 5 oxychloride can be described by the following equation: If the interaction of the molecule with the surface is weak (Van der Waals forces). . that under a given experimental condition the most stable chemical state is formed and that this states exists during the entire experiment.228 The Chemistry of Superheavy Elements (with lower coordination) of the adsorbed particles to the modified surface and the bond to the surface of the pure macroscopic phase of the compound. This is typical for physisorption. the molecule remains unchanged regarding its binding structure. in the simplest case. Adsorption data from more recent experimental results were evaluated applying the model of mobile adsorption [4]. For example. Correlations based on estimated standard sublimation enthalpies allow pre­ dictions of adsorption enthalpies for selected compounds for the case of zero surface coverage. For gas chemical studies we assume. data from previous experiments were re­ evaluated using this model. Thus. which may occur with very high reaction rates. obtaining similarly modified stationary surfaces. All deposition and volatilization processes of single atoms or single molecules (the nearest case to zero surface coverage) are basically adsorption and desorption processes. the restoration of the most stable chemical state is possible and is realized very fast. These adsorption processes are accompanied by changes of the coordination number of the central atom and.

6. Empirical Models in Gas-Phase Adsorption Chromatography 229 .

The oxidation state remains unchanged. Empirical Calculation Methods for Adsorption Enthalpies 3. which is involved in the mechanism of the adsorption reaction [45. If the elements 112 and 114 have a noble-gas like character [62]. in a fictitious solid state. 3. can be calculated with this method [61].8]. the substitutive adsorption of a group 4 tetrachloride is described by: The knowledge of the type of the adsorption process is crucial for the determination of the adsorption enthalpy from experimental results. This is a typical case of chemisorption. for the oxyhydroxide compound of a metal ion in the oxidation state 6+ the dissociative adsorption can be described by [7]: As another example. where adsorption enthalpies can be calculated using empirical and semi-empirical relations. break of a double bond). . in a different kind of a chemisorption process a reversible change of the oxidation state or a reversible change of the number of ligands or even the nature of ligands may occur during the adsorption and the desorption of a molecule. (ii) Secondly. For physisorbed noble gas atoms a roughly uniform distance to different surfaces of about 2. For example. In the case of atoms with a noble-gas like ground-state configuration and of symmetrical molecules the binding energy to a solid surface can be calculated as a the ionization potential the distance function of the polarizability (R) between the adsorbed atom or molecule and the surface. then.47±0.1 VAN DER WAALS INTERACTION Depending on the type of interaction between an adsorbed particle and a solid state surface there are cases.230 The Chemistry of Superheavy Elements by a changes of the type of binding (e. for example on quartz. they would form non conducting colorless crystals. and the relative dielectric constants (Method 9) [58-61]: The binding energy approximately equals the adsorption enthalpy. A physisorptive type of adsorption may occur and their adsorption properties.2 Å was deduced from experimental results [63]. see Table 3.g. One experimental approach to gain this information is by varying the partial pressure of the reactive carrier gas.

73]. which depends on the nature of both metals. see Figure 9: For real metals this value is close to 1. The relative difference between the dissociation enthalpy of two-atomic elemental molecules given by Gurevic [64] and the sublimation enthalpy of these elements [65] from Method 1 can be used to estimate the metallic character (m) of elements (Method 10) [28]. Data for these calculations are given in [34. for example. the desublimation enthalpy is an exclusive property of the adsorbate. For the calculation of the net adsorption enthalpies of transactinides on metal surfaces the partial molar enthalpies of solution and the enthalpy of displacement are required. the net adsorption enthalpy characterizes the interaction. The adsorption enthalpy equals the sum of desublimation enthalpy and net adsorption enthalpy. One general rule of the periodic table is that the metallic character of the elements increases with increasing atomic number Z along the groups of s-elements and of p-elements.72. These values can be obtained using the semiempirical Miedema model [66-70] and the Volume-Vacancy or SurfaceVacancy model [32. Element 117. then the periodic order scheme describing the adsorption of metallic elements will also accommodate this transactinide element. According to this relation a metallic character can also be expected for the elements 112 and 114 [28]. The net adsorption enthalpy is the enthalpy difference between a pure solid compound and its adsorbed state on a surface at zero surface coverage. This value shows qualitatively if the (non metallic association to homo-nuclear two-atomic molecules character) is energetically preferred over the formation of a coordination lattice (metallic character) and vice versa. Empirical Models in Gas-Phase Adsorption Chromatography 231 3. Hence.2 ADSORPTION OF METALS ON METAL SURFACES If the contact of a transactinide atom with a metallic surface leads to the formation of metallic bonds. On the other hand. can be assumed to have a semi-metallic character.70.71]. .6.

. can be used as stationary phase in gas adsorption chromatographic experiments for selective gas chemical separations or. as strong fixation materials for the sample preparation in the measurement of transactinides. which are presented in Table 4. The experimental investigation of the metallic or non-metallic nature of the elements 112 and 114 represents an interesting and challenging scientific task.232 The Chemistry of Superheavy Elements The net adsorption enthalpies and the predicted sublimation enthalpies (see Method 1) were used to calculate the adsorption enthalpies of transactinides on selected metal surfaces (Method 11). in the case of high adsorption interaction. The metals.

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66. ZfK-396.: J... 70..R. In: Zentralinstitut für Kernforschung Report. 71. (1976) 237. Less-Common Met. (1975) 183.R.R. Berlin.6. 46. R.: J. 67. In: Labor für Radio ­ und Umweltchemie Annual Report 2000.R. R.: J. Villigen (2001) 7. 69. Hesselmann.. 32. F. Eichler. (1985) 131.: "The Interaction of Element 112 with Metal Surfaces".Less-Common Met.R. A.Thermochemical Properties of Inorganic Substances. Acta 38. Boom. De Boer. 73..: . Miedema. A. (1973) 117. ed. (1991). Miedema.. O. Eichler..R. 41.. Boom. De Boer. O. Rossendorf. 68. F. Eichler. A. Paul Scherrer Institut Villigen (2000). (1976) 67. Less-Common Met. Miedema. (1979)..Metallchemie der Transactinoide“. B. Springer-Verlag.: Radiochim. Miedema. Eichler. K. B.: J. 72. Empirical Models in Gas-Phase Adsorption Chromatography 235 65. B.: "Bestimmung der Adsorptionswärme gasförmiger Metalle auf festen Metalloberflächen bei Nullbedeckung (Empirisches Modell)".Less-Common Met. Knacke. A. B. . Kubaschewski. 45. PSI-Report 00-09.

221 207. 232 Miedema model 231 Monte-Carlo simulation 212. 226. 223. 227. 231 Enthalpies 220. 232 Sublimation enthalpy 222. 230 221. 229. 217 Exponential integral function 209 Formation 219. 227. 221. 229 Gas thermochromatography 209 Isothermal gas chromatography 208 Metallic character 231. 222. 231 Phonon frequency 208 Physisorption 228 Pprediction 220. 227. 228. 227. 230.236 Index The Chemistry of Superheavy Elements Adsorption 219. 226. 225. 220. 224. 209. 227. 217 Periodic table 220. 227. 232. 228. 228. 210. 227. 231. 230. 226. 231 Surface 219. 228. 228. 225. 224. 230 Partition coefficient 207. 228. 232 Surface coverage 220. 223. 220. 227. 225. 215 Net adsorption enthalpy 220. 223 Standard states 207. 232 Equilibrium constant 207. 222. 225. 231 Surface-Vacancy-model 231 Thermochemical data Transport velocity Chemisorption 230 Conductivity of the column 210 Correlations 220. 220. 209 Stationary phases 219. 225. 223. 225. 226. 210 231 Vacuum thermochromatography 210 Van der Waals forces 228 Vapour pressure 225 Volatility 219. 217 Dissociation 222. 228 Radii 219. 213. 226 Radii-volatility correlation 226 Random numbers 212 Relativistic 221 Standard formation enthalpies 221. 231. 231 Gas adsorption chromatographic process 219. 230. 228 Diffusion coefficient 214. 221. 227. 208. 220 Gas phase 219. 226. 222. 231. 220. 234 . 229. 211. 234 Binding energy Noble gas 230 Oxidation state 223. 226.

Second. Switzerland Labor für Radio. the very first investigation of rutherfordium has been conducted in form of frontal isothermal gas chromatography in a chlorinating atmosphere [1]. Türler c a b Labor für Radio.b. They include modest chemical separation factors 237 M. Schädel(ed. Already. Paul Scherrer Institut. gas phase separation procedures play an important role. production of transactinides at accelerators implies a thermalization of the primary products in a gas. A. 237-289. Printed in the Netherlands. Gäggeler a. D-85748 Garching. All these advantages compensate for some disadvantages if compared to liquid-phase separations.Chapter 7 Gas-Phase Chemistry H. Third. .W. The success of gas chemical separations in transactinide research is quite remarkable since gas chromatography is. There are several reasons for this exceptional situation. gas phase separation procedures are fast and may be performed in a continuous mode. at the exit of the chromatographic column separated volatile species can be easily condensed as nearly weightless samples on thin foils.). Technische Universität München. The Chemistry of Superheavy Elements. First. This enables detection of decay and spontaneous fission (SF) of the separated products with supreme energy resolution.und Umweltchemie. Introduction In transactinide chemistry research. CH-5232 Villigen PSI. Switzerland c Institut für Radiochemie. Germany 1. CH-3012 Bern. usually helium. of minor importance in inorganic analytical chemistry.und Umweltchemie. in general. It is rather straightforward to connect such a recoil chamber to a gas chromatographic system. © 2003 Kluwer Academic Publishers. Universität Bern.

1 VOLATILE COMPOUNDS OF GROUP-4 ELEMENTS Due to the high sublimation enthalpies of group-4 elements. chlorides and bromides . A good measure of the volatility is the vapor pressure. most gas chemical investigations of this element have been conducted in form of its chloride. This observation is not surprising. mostly in form of chlorides and bromides or oxychlorides and oxybromides. Only in one experiment an attempt was made to search for a p-element behavior of Rf. Under halogenating conditions. respectively. proved to be ideal for the 6d elements of groups 4 to 7. In addition. the experiment yielded no evidence for a “d-like” “Pb-like” behavior of Rf [4]. gas chromatographic separations of the atoms are not feasible in quartz columns. Figure 1 depicts the vapor pressure curves for Zr and Hf halides in the gas phase over the respective solids. mostly inorganic compounds have been synthesized and separated such as halides and oxyhalides. also the oxide/hydroxide molecules have been synthesized. the tetroxide is the species of choice. based on a predicted ground state configuration of or. Evidently. the volatility decreases according to with M= Zr and Hf. One should keep in mind that the retention temperature regime in quartz chromatography columns is limited to maximum temperatures of about 1000 °C. 2. As can be seen. For future studies with the pelements around atomic number 114 the elements are expected to be volatile in their atomic state and should behave like noble metals or even like a noble gas. however. due to the short half-lives of transactinide nuclides. since this molecule is very volatile. This class of compounds. chlorides. Rutherfordium (Rf. oxychloride or bromide. So far. since MultiConfiguration Dirac-Fock (MCDF) calculations showed that ionization potentials. Element 104) So far. 2. the kinetics of the formation of chemical compounds should be fast.238 The Chemistry of Superheavy Elements and a rather limited number of volatile species that are suited for gas chromatographic investigation. group-4 elements form mono­ molecular pure halides such as tetra fluorides. atomic and ionic radii for Rf are very similar to those of Hf [3]. from a more recent calculation rather than the expected However. For elements of group 8. For the group 6 and 7 elements. bromides and iodides.

They were molecules. However. It was kept at lower temperatures in order to adsorb the assumed that the produced isotopes of Rf decay at least partly by spontaneous fission. As a chlorinating agent 0. In these pioneering studies isothermal frontal gas chromatography experiments showed that in a chlorinating gas Rf forms a highly volatile molecule. An alternative process is substitutive adsorption of the pure halides on the surface of the quartz chromatography column where oxychloride formation is possible in the adsorbed state only. It was observed that tetrachlorides and the oxide under elevated temperatures [6].7. Iodides have the disadvantage of a poor thermal stability and fluorides are least volatile.2 EARLY GAS CHEMICAL STUDIES WITH RUTHERFORDIUM The first chemical study of Rf [1] was part of the discovery claim of this element by scientists from Dubna. 2. see Figure 8 in Chapter 4.15 mm Hg vapor pressure of was added to a flowing carrier gas. Gas-Phase Chemistry 239 are clearly the best choices for gas chemical studies. The gas then passed through an isothermal glass column kept at temperatures between 250 and 300 °C. From previous experiments it was known that actinides do not form sufficiently volatile chlorides that could pass the column at such moderate temperatures. Behind the column mica solid state detectors were positioned. In principle. for group-4 elements little is know about these and decompose to compounds. Mica is known to be well suited for identification of . For production of the isotopes the hot fusion reaction was used. in oxygen containing carrier gases also oxyhalides can be synthesized.

of -110 kJ/mol and –146 kJ/mol for Rf and Hf on the quartz chromatography column surface were deduced [8].240 The Chemistry of Superheavy Elements latent fission tracks. which permits to compare the volatility of the Rf species. It was therefore concluded that with a half-life of 3 s and an assumed small fission branch was the isotope that labelled the separated molecule. this assignment was questioned since additional measurements proved that this isotope has a half-life of only 20 ms. After these very first experiments the Dubna group applied the thermochromatography technique. therefore convincingly proving that Rf is a d element [7]. see also Chapter 4. These fission events were assigned to a spontaneously-fissioning isotope of Rf. From the observed very similar deposition temperature of the Rf and Hf chlorides it was concluded that both elements behave very similarly. the standard enthalpies of adsorption. presumably Later. with those of the Hf compounds. Based on some assumptions on the adsorption process and assuming that indeed the decay of with a half-life of 3 s was detected. An example of such a study is depicted in Figure 2. . measured via the deposition temperature in the chromatographic tube. In a series of experiments that accumulated a total beam dose of beam particles 65 fission tracks were detected along the mica detectors. too short for chemical study. Recently. the chromatographic peaks shown in Figure 2 have been analyzed applying a Monte-Carlo model.

Simultaneous formation of Hf isotopes may be obtained by covering the target by a thin layer of Gd. novel devices have been developed such as the On. It has a half-life of 78 s and can be produced in the Cm at a bombarding energy of about 100 MeV. As ”reactive” gas. Improved versions of OLGA (versions II and III) enabled the applications of corrosive gases such as hydrogen chloride or hydrogen bromide. 2. . see also Chapter 4.3. Model studies with the p-elements Po. chlorine.Line Gas chemistry Apparatus (OLGA) [10] or.2 Isothermal gas chromatography studies of and For investigations of the chlorides and bromides commonly the isotope was used as a tracer. Gas-Phase Chemistry 241 Thermochromatography was also applied to investigate the volatility of Rf and Hf bromides [9].3.7. Pb. in a modified version. respectively. To reach this ambitious goal. This technique offers the possibility to combine a continuous separation of volatile species with an in-situ detection of the products on the basis of single atom counting. These experiments yielded evidence that Rf bromide is more volatile than Hf bromide. OLGA I was restricted to an operation with inert gases. On-lineisothermalgas chemistry has originally been developed to search for superheavy elements with atomic numbers between 112 and 118. 2. fusion reaction via to a longdecays via emission of two sequential lived product. Bi and At showed that at temperatures of up to 1000 °C excellent separations of these elements from d elements and from f elements could be achieved.1 General remarks In recent years predominantly continuous isothermal chromatography has been applied in gas chemical studies of transactinides. and also more volatile than Rf chloride. Hence. This made it possible to synthesize volatile halides and measure their retention times in isothermal quartz columns. Its application concentrated on separations of volatile atoms. identification of after chemical separation bases energies of the on the measurement of the two lifetimes and two mother and its daughter nuclide. the Heavy Element V olatility Instrument (HEVI) [11]. thionyl chloride or boron tribromide vapor etc.3 ON-LINE ISOTHERMAL GAS CHEMICAL INVESTIGATIONS OF RUTHERFORDIUM 2. From the four signals an unequivocal identification of every decaying atom of rutherfordium may be achieved. traces of hydrogen gas could be added to a helium carrier gas in order to stabilize the elemental state.

and Rf were (Zr. since the higher volatility of compared to that of is unexpected on the basis of classical extrapolations.242 The Chemistry of Superheavy Elements Figure 3 depicts the result from such a study with the OLGA III device [12]. In an earlier study with the device HEVI chlorides of Zr. purified from traces of oxygen. the volatility of Zr chloride turned out to be very similar to that of Rf chloride. In addition. different to the volatility of Hf chloride. Hf) and HC1 (Rf). The chemical reagent was HCl gas. For Rf and Hf chlorides the same sequence in volatility was found as depicted in Figure 3. Hf. In contact with forms a very volatile molybdenum oxychloride that passes HCl. hence. This observation is rather unexpected. investigated employing the reactive gases particles in a He carrier gas served as aerosol [13]. since the volatilities of macro amounts of Zr and Hf tetrachlorides are nearly identical. Helium saturated with carbon particles served as carrier aerosol to transport the products from the collection chamber to the chemistry device. Rf passes through the quartz column at a lower retention temperature compared to Hf. see Figure 1. through the chromatographic column without deposition on its surface. added to the carrier gas at the entrance of the oven system. This observation received considerable attention and was interpreted as evidence for relativistic effects. .

It was speculated that the oxychlorides do not exist in the gas phase but only in the adsorbed state. and were found to decompose to the tetrachlorides at elevated temperatures [6]. In a more recent study with HEVI.7.3. In thermochromatography experiments an increase of the deposition temperature of Zr and Hf was observed as a function of the partial pressure of oxygen in a chlorinating reactive gas mixture [16]. For the transport KC1 was used as served as a reactive gas. 2.3 Oxychlorides of Rf The oxychlorides of group-4 elements are expected to be less stable than the pure chlorides. In addition. An OLGA III study with oxygen containing chlorinating reactive gas confirmed this observation: Rf and Hf compounds were considerably less volatile compared to oxygenfree conditions. Rf aerosol particles and bromide was found to be less volatile compared to the Rf chloride. The behavior of Zr and Hf bromides were found to be very similar being less volatile than the Rf bromide [15]. The following transport mechanism was proposed: . see Figure 5. whether and exist in the gas phase. these findings were essentially confirmed. using KBr particles and HBr as a brominating agent. It is therefore not clear. see Figure 4. Gas-Phase Chemistry 243 A first study of Rf bromide with OLGA II indicated that the Rf compound is more volatile than Hf bromide [14].

. Figure 6 summarizes resulting values from isothermal gas chromatographic investigations of the pure chlorides and bromides of Zr. as seen in Figure 5. Hf. using the HEVI and OLGA II devices [19]. In addition. Hf. The experimental values for Rf show a striking reversal of this expected trend. and Rf.244 The Chemistry of Superheavy Elements It is interesting to note that. respectively. the bromides have more negative values. much more similar compared to the pure chlorides and and behave 2.3. and Rf chlorides and bromides on quartz From the measured chromatographic retention temperatures adsorption of single molecules on the surface of the quartz enthalpies chromatography column can be deduced.4 Adsorption enthalpies of Zr. hence being less volatile than the corresponding chlorides. In addition. This analysis is based on certain thermodynamic assumptions of the adsorption process of single molecules with the surface of the chromatographic column [17]. A smooth values from Zr through Hf shows that (classical) extrapolation of the one would expect the values for or to be more negative than those of the respective Hf compounds. a Monte Carlo model enables to describe the migration path of each single molecule along the chromatographic column under real experimental conditions [18].

Element 105) Dubnium is expected to have a electronic ground state configuration. This makes dubnium a firm member of group 5 of the Periodic Table. Gas-Phase Chemistry 245 Relativistic calculations of the chemical properties of these compounds predict trends that are in agreement with experimental observations. 3. in addition. gas chemical investigations were only successful if the quartz chromatography columns were very carefully preconditioned with the halogenating reactive gas prior to each experiment and. As a general rule. see Chapter 2.7. All gas chemical investigations of dubnium have been performed with in form of the pentahalides (chlorides and bromides) and oxyhalides. all these studies were extremely difficult due to the high tendency of group-5 elements to react with trace amounts of oxygen or water vapor. . Therefore. it was argued that this “reversal” in the trend of for chlorides and bromides when going from Zr via Hf to Rf is evidence for “relativistic effects” in the chemistry of Rf [12]. Hence. positioned below tantalum. Dubnium (Db. applying extensive cleaning procedures to the carrier gas to remove trace amounts of oxygen and water vapor.

Besides the pure halides. see Figure 8. followed by the pentachlorides and the pentabromides. They should be less volatile compared to the pure halides. see Figure 7.246 The Chemistry of Superheavy Elements VOLATILE COMPOUNDS OF GROUP-5 ELEMENTS 3. . This was confirmed experimentally for niobium.1 Group-5 elements are most stable in their maximum oxidation state +5 and therefore form pentahalides. also the oxyhalides are stable in the gas phase. Most volatile are the pentafluorides.

This nuclide was produced in the Db reaction. see also Chapter 4.2 EARLY GAS CHEMICAL STUDIES WITH DUBNIUM As early as 1970 gas chemical experiments with Db were performed in a chlorinating atmosphere [20]. . These investigations were performed with which has a small fission branch.7. see Figure 9. These studies applied the gas thermochromatography technique. Gas-Phase Chemistry 247 3. Later studies were conducted in a brominating gas medium and again yielded evidence that Db bromide is less volatile compared to the homologues compound with Nb [21]. and they indicated that the deposition temperature of Db as a chloride (or oxychloride) is rather similar to that of Hf under identical conditions and significantly higher compared to the deposition temperature of Nb.

. despite very thorough cleaning procedures.1 Production of dubnium isotopes On-line gas chemical studies of dubnium have been mostly performed with This nuclide can be produced in the reaction at a beam energy of about 100 MeV.3. identification of each separated labeled molecule is and their lifetimes based on either detection of two characteristic or on the detection of a spontaneous fission decay.3.248 The Chemistry of Superheavy Elements From the result of this experiment it was concluded that the boiling point of may exceed the boiling point of by 80-100 °C and may be close to the boiling point of The ionic radius of was estimated to be close to the radius of which is . Obviously. Hence. It has a half-life of 34±5 s and decays with 67 % by emission of two sequential to the longvia lived In addition. most likely Figure 10 depicts a measured chroma­ tographic curve in conjunction with the data for Nb from Figure 8 [22]. minute amounts of oxygen and/or water vapor in the system were still sufficient to form at least partly dubnium oxychloride.2 Chlorides and oxychlorides Several attempts failed to form the pure pentachloride of Db in on-line isothermal gas chromatographic investigations. has a spontaneous fission decay branch of 33%. 3. whereas the radii of and are both 3.3 ON-LINE ISOTHERMAL GAS CHEMICAL INVESTIGATIONS OF DUBNIUM 3.

The two species are tentatively assigned to and respectively. a species with a lower volatility passing through the column above 350 °C and one with a higher volatility that is retained in the column only below 200 °C. must be equal or more volatile than see From this follows. purified with activated charcoal at 900 °C.3 Bromides and oxybromides The volatility of Dubnium bromide was studied with HBr as a reactive gas using the isotope formed in the reaction [23]. Obviously.3. Evidence for a lower volatility of dubnium bromide relative to that of niobium bromide has already been found in previous thermochromatographic studies. It is interesting to note that none of the gas chemical investigations succeeded to investigate the behavior of tantalum chloride. the tendency to react with oxygen is even higher for Ta compared to Nb and Db. A trend in volatility of was deduced. The data are shown in Figure only when HBr was saturated with 11. the volatile tantalum bromide was formed vapor. that Figure 3. . see Figure 9. The shape of the yield curves suggests two components. 3.7. Gas-Phase Chemistry 249 As chlorinating agent HCl gas was used. Interestingly. This sequence is very surprising since is expected to be more volatile compared to and respectively. In this experiment the retention behaviors of niobium and tantalum bromides were investigated as well.

presently it remains open whether the values for Db shown in Figure 12 represent the behavior of the pure halides or of the oxyhalides. Db has a much higher tendency to react with oxygen compared to the lighter homologues Nb and Ta. 27] and further studies of the behavior of homologues elements Mo and W [28]. Seaborgium (Sg.9 s was the longest-lived known Sg isotope. If true.3. 4.250 The Chemistry of Superheavy Elements 3. Element 106) For over 20 years. this would mean that under identical gas chemical conditions Nb and Ta form pure bromides while Db does not. It is rather surprising to observe a different trend of the values when going from Nb via Ta to Db. In addition to the minute production rates. from Dubna studied the chemical identification of Sg as a volatile oxychloride making use of an on-line thermochromatography method [25]. with a half-life of 0. bromides and oxybromides on quartz Figure 12 depicts values of group-5 chlorides and bromides measured with the OLGA technique (for an overview of several experimental investigations and a re-analysis of the data. Timokhin et al. So. if compared to the situation in group 4 depicted in Figure 6. that e. an international collaboration of chemists conducted on-line . oxychlorides.4 Adsorption enthalpies of Nb. see [24]).g. In 1992 S. However. Shortly thereafter. in case of the bromides [23] the oxybromide of dubnium has been formed rather than the pure pentabromide. It was speculated [24]. this short half-life effectively prevented a chemical identification of Sg. This claim was substantiated by ancillary experiments [26. Ta and Db chlorides.

Mo. . W. whereas the existence of is doubtful. In the elemental state all group-6 elements are extremely refractory. Cl) exist. Of the pentahalides the pentafluorides and the pentachlorides are known. W). is monomeric in the gas phase. a first thermochemical property of a Sg compound. and are known. While structure of the pentafluorides. however. 4. oxide hydroxides. two stoichiometric types The Mo compounds are less stable than those of W. Sg was also characterized as volatile oxide hydroxide in on-line isothermal chromatography experiments [31]. can be volatilized as a monomeric vapor while is decomposing to on moderate heating. decomposes to disproportionates at temperatures above 200°C to form and are unstable However. already at room temperature. W also and have the typical tetrameric forms the pentabromide. genetically linked. The presence of Sg after chemical isolation in the gas-phase was established by directly identifying the nuclides and via the observation of their characteristic. Both Mo and W have a wide variety of oxidation states and their chemistry is among the most complex of the transition elements. In contrast to the pure halides. Recently. Also. and W. Mo and W form volatile halides. and also carbonyls. and form dimeric species in the solid.1 VOLATILE COMPOUNDS OF GROUP-6 ELEMENTS Seaborgium is expected to be a member of group 6 of the Periodic Table and thus homologues to Cr. For the 6+ oxidation state the and (M = Mo. The melting and boiling points are strongly increasing down the group (W has the highest melting point of all metals). nuclear decay chains [29]. While both Mo and W are chemically very similar. Gas-Phase Chemistry 251 isothermal chromatography experiments with Sg oxychlorides [29]. Of the oxyfluorides and are known. X = F.1. there is not much similarity with Cr. oxyhalides.1 Halides and oxyhalides Among all hexahalides only the compounds (M = Mo. is not stable and exists probably only in a chlorine atmosphere in the gas phase. Of the oxychlorides all four varieties exist. namely the adsorption enthalpy of Sg oxychloride on the chromatographic surface was measured in these experiments [30].7. There exist a number of volatile inorganic Mo and W compounds that are suitable for gas chromatographic investigations. the oxyhalides of group-6 elements are more stable and show a similarly high volatility. there is no indication that single molecules of even at elevated temperatures. 4.

W) should be the main excess of oxygen the trioxides component. W) can be oxygen the more volatile oxide hydroxides formed.1. W. Br) are known. X = Cl. The volatility of is and higher than that of whereas the situation is reversed for W. whereas the heavy actinides and the transactinides Rf and Db do not form volatile oxides and oxide hydroxides.2 Oxides and oxide hydroxides By analogy to Mo and W the oxides and oxide hydroxides of Sg are expected to be moderately volatile. carrier-free preferentially as polymers of the type amounts can be volatilized in dry oxygen only as monomers. The vapor pressure of the pure chlorides all are very similar. This sublimation.252 The Chemistry of Superheavy Elements In the 5+ oxidation state four principal compounds of the type (M=Mo. Mo and W form many stable oxides. change in the sequence of vapor pressures can be explained by the solid phase entropies. Macroscopic amounts of and sublimate However. where According to tabulated enthalpies of is more volatile than should be more volatile than [32]. but in (M = Mo. The vapor pressure of Mo and W chlorides and oxychlorides over their respective solids as a function of temperature is shown in Figure 13. Extensive studies using thermochromatography and on-line . For this reason this class of compounds should be very selective with regard to a gas chromatographic isolation of Sg from the plethora of by-products of the nuclear formation reaction. In moist (M=Mo. 4.

Volatile as a oxychlorides were synthesized by adding air saturated with reactive agent.9 s chemically identify Rf and Db was used.2 GAS CHEMICAL STUDIES WITH SEABORGIUM 4. the reaction was A very similar set-up as in experiments to employed to produce 0. in several experiments a number of SF tracks were found in the column in the temperature region 150 .1 Thermochromatography of oxychlorides Early on. In Figure 14 the location of those 41 registered SF events are shown that were observed in the . W 4. separation procedures to chemically isolate Sg concentrated on inorganic gas chromatography of chlorides and/or oxychlorides [36]. The deposition of Sg was registered after completion of the experiment by searching for latent SF tracks left by the SF decay of Indeed. In a number of studies the gas chromatographic behavior of halide and oxyhalide species of Mo and W were investigated with respect to a physico-chemical characterization of Sg [37-45]. Sg must form volatile oxychloride compounds. was absent. and finally deposited according to their volatility. In contrast to earlier experiments. like its lighter homologues Mo and W. However. direct production of carbonyls from the elements and CO is only — if at all — accomplished at high pressures and temperatures. to which a longitudinal. The SF tracks were only found. Therefore. Mo. In experiments by the Dubna group [25-28]. no mica plates were inserted. 4. but the fused silica column itself served as SF track detector.3 Carbonyls A characteristic feature of d-group elements is their ability to form type ligands such as CO. This was attributed to the increased surface and thus a much longer retention time. negative temperature gradient was applied. which was inserted as a filter for aerosols.1. They were attributed to the decay of Sg nuclides. The formed oxychloride species migrated downstream the fused silica chromatography column.2. All group-6 elements complexes with Cr. and W form very volatile and stable hexacarbonyls and constitute the only complete family of carbonyls.7. when the quartz wool plug. Reaction products were thermalized behind the target in a rapidly flowing stream of Ar gas and flushed to the adjoining thermochromatography column. Gas-Phase Chemistry 253 isothermal chromatography [33-35] in dry and moist oxygen have revealed that the transport of Mo and W in moist oxygen is not governed by simple but by a dissociative reversible adsorption reactions of adsorption according to the reaction M = Mo.250 °C.

Sg) or (M = Mo.254 The Chemistry of Superheavy Elements course of three experiments corresponding to a total beam dose of beam particles. Sg) within group 6 was obtained. The dotted histogram shows the data corrected for the relative detection efficiency due to the annealing of fission tracks at elevated temperatures. W. Sg) molecules are formed and in a second. slower step the deposited is converted to more volatile Therefore the Sg deposition peak was attributed to the compound whereas the deposition peak was attributed to Due to the occurrence of two different species as well as due to the large differences in half-life no information about the relative volatility of (M = Mo. Based on the results of ancillary experiments with short-lived W nuclides. and — adsorbed to their . 30].2 Isothermal chromatography of oxychlorides In 1995 and 1996 an international collaboration of radiochemists conducted on-line isothermal chromatography experiments with Sg oxychlorides using the OLGA technique. Section 4. recoiling from the target.3. 4. at the Gesellschaft für Schwerionenforschung (GSI) in Darmstadt [29. were stopped in He gas loaded with carbon aerosols. The solid lines denoted with "[106]" and with show the and the expected shape of the "[106]" deposition peak for 2. see Chapter 4. it was concluded that in a first. fast step volatile (M = W.2. W. In this work the longerlived Sg-isotopes and were synthesized in the reaction Nuclear reaction products.5 h deposition peak fitting the SF data.

Simultaneously. Without changing any of the other experimental parameters. For kJ/mol was deduced. In a second experiment at 350°C isothermal temperature. W. whereas the yield curve for was determined in an earlier measurement. In order to assure that the experimental set-up performed as expected. whereas for kJ/mol resulted. The aerosols carrying the reaction products were collected on quartz wool inside the reaction oven kept at 1000°C. the was isothermal temperature was then lowered to 250°C and the yield of measured with a comparable sensitivity as at higher isothermal temperatures. see Chapter 4. 350°C and 400°C are summarized in one data point). In order to increase the sensitivity of the experiment the motherdaughter recoil counting modus was implemented at the rotating wheel system ROMA. Reactive gases — and traces of — were introduced in order to form saturated with volatile oxychlorides (thermodynamic calculations [44] indicate that Mo and W most probably form the dioxide dichloride M = Mo. namely error interval).7. In Figure 15. Gas-Phase Chemistry 255 surface — continuously transported through a thin capillary to the OLGA set-up. The sequence (M = Mo. The yield curve for was measured with the same chromatography column and under the same experimental conditions as they were then used for the isolation of Sg. From the measured Sg data a first thermochemical property of a Sg kJ/mol (68% compound could be deduced. Sg) on the stationary phase is in volatility of The probability that is equally volatile or even more volatile than was estimated to be less than 15%. the nuclide was simultaneously produced from a small admixture to target material and its yield was monitored. Section 4. W. the the relative yields measured for oxychlorides of short-lived Mo. the carbon aerosols were converted to The chromatographic separation takes place downstream in the adjoining isothermal section of the column. and Sg nuclides are shown as a function of isothermal temperature (the Sg data points measured at 300°C. W). The solid lines show the results of a Monte Carlo simulation procedure where the migration of a molecule through the chromatography column has been modeled [47]. At temperatures of 300°C and above group-6 oxychloride molecules travel through the column essentially without delay. the results of the first experiment were confirmed by observing further chains [46].3. In a first experiment conducted at isothermal temperatures of the chromatography column of 300°C and of 400°C the nuclide was unambiguously identified after chemical isolation by the observation of its chains [46]. .

4. and presumably also Sg.2. Section 2.g. the longer-lived isotope produced in the reaction was used despite its . is a very important quantity in order to estimate e. in experiments to characterize Sg as an oxide hydroxide.3. in moist oxygen containing gases occurs via a dissociative adsorption reaction and not via a simple reversible adsorption. were directly correlated with their macroscopic see Chapter 6. It was sublimation enthalpies therefore possible to directly estimate kJ/mol from only a few investigated molecules. the least volatile element in the an equally or even higher Periodic Table. Therefore. Part II. Retention times for these dissociative processes in an isothermal chromatography column are generally longer.3 Isothermal chromatography of Sg oxides/oxide hydroxides The transport of group-6 elements Mo. Seaborgium is expected to have than W. W.256 The Chemistry of Superheavy Elements The experimentally determined measured with trace amounts (at zero surface coverage). even at very high temperatures. With the High Temperature On-Line Gas Chromatography Apparatus (HITGAS) [48] retention times of about 8 to 9 s were determined from measurements with short-lived Mo and W nuclides at isothermal temperatures above 1270 K.

the relative yields of Mo and W oxide hydroxides in open quartz columns using humid as reactive carrier gas component are shown as a function of isothermal temperature. compared to the shorterlived produced in the 5n evaporation channel with a maximum cross section of about 240 pb [46. due to the thickness of the metal foils. Section 4. The search for genetically linked decay chains revealed two candidate events. as expected. The solid lines are the result of a Monte Carlo model based on a microscopic description of the dissociative and adsorption process [34] with The dashed line represents a hypothetical yield curve assuming that group-6 oxide hydroxides are [31]. since. see Chapter 4. Reaction products recoiling from the target were stopped in He gas loaded with aerosol particles and swept to the HITGAS set-up. Fortunately. Furthermore. which makes detection of chains difficult. In an experiment conducted at GSI a target was bombarded with 119MeV ions. The probability that both of these events were entirely random was only 2%. In the element properties. the time-consuming reclustering step could be avoided. In Figure 16.7. presumably as Sg oxide Sg showed typical group-6 hydroxide. Gas-Phase Chemistry 257 lower production cross section of only about 60 pb. Sg appeared to be volatile under the conditions of the experiment. Under the given conditions this coincides also with a U(VI)-like behavior. transported by simple reversible adsorption with . Therefore. At the entrance to the chromatography column moist was added to the gas-jet.49]. final samples could be assayed only in a geometry. Loosely packed quartz wool in the reaction zone served as filter for aerosol particles. decays by genetically linked particle emission to the relatively short-lived which decays by spontaneous fission (100%). A total beam dose of ions was accumulated. The temperature of the quartz chromatography column was 1325 K in the reaction– and 1300 K in the isothermal zone. However this reduced the detection efficiency. By condensing the separated volatile species directly on metal foils mounted on the circumference of the rotating wheel of the ROMA detection system. U is also known to form a volatile oxide hydroxide.3. contaminants like various Po isotopes cannot be removed in the oxide/hydroxide chemical system.

258 The Chemistry of Superheavy Elements In order to answer the question about the sequence of volatility of oxide hydroxides within group 6. paved the way to the first successful chemical identification of Bh as oxychloride compound [54]. The decay properties of the nuclides were entirely unknown at the time. and Re and thus to belong to group 7 of the Periodic Table. due to the very low formation cross sections of only about 70 pb for (produced in the reaction [52]. any experiment aiming at a chemical identification of Bh was predestined to be a "tour de force". For the synthesis of Bh nuclides the reactions and were employed. and With the recent identification of the nuclides [52] in bombardments of with ions and the recognition that the rapid formation of volatile oxide hydroxides is apparently hindered [53]. However. in . R. Element 107) The fourth transactinide element bohrium is expected to be a homologue of Mn. further experiments have to be conducted at lower isothermal temperatures. Bohrium (Bh. Eichler et al.51]. Tc. 5. Nevertheless. Two early attempts to chemically identify Bh as volatile oxides or oxide hydroxides failed [50.

1 Oxides and oxide hydroxides Oxides and oxide hydroxides of Tc and Re are typically formed in an containing gas phase. Eichler et al. an international collaboration of radiochemists observed a total of 6 chains originating from after chemical isolation and established the sequence in volatility 5. An increased stabilization is observed for the half-filled d-shells. Some typical mononuclear compounds of group-7 elements are listed in Table 1. Gas-Phase Chemistry 259 a one month long experiment conducted at the Paul Scherrer Institute (PSI). Compounds of Mn are chemically most stable in the oxidation state +2 whereas compounds in the oxidation states +4 and +7 are strong oxidizing agents. Of all the compounds listed in Table 1 the oxides. mostly using the method of thermochromatography [56-67].1 VOLATILE COMPOUNDS OF GROUP-7 ELEMENTS In contrast to elements in groups 4 and 5. and the oxychlorides turned out to be the most promising candidates for a chemical separation and identification of bohrium. which is especially evident for the 3d shell of Mn. They were extensively studied. The technique has also been applied to develop Tc and Re generator systems for nuclear medical applications [68. but similar to group 6.1. In their works. which is considerably more volatile than its neighbors Cr and Fe in the same period. Compounds of Tc and Re in high oxidation states are much more stable towards reduction and the oxidation state +2 is of minor importance. atomic and ionic radii of Tc and Re are very similar and thus these elements are chemically very much alike. [70] and R. Due to the lanthanide contraction. the 7 valence electrons of group 7 elements allow for a large number of stable oxidation states and thus a wide variety of inorganic compounds. Schädel et al.69]. [53] studied the oxide and the oxide hydroxide chemistry of trace amounts of Re in an system with respect to its suitability for a first gas chemical identification of Bh. oxide hydroxides. Switzerland. M. However. Mn behaves chemically markedly different from its homologues Tc and Re. They investigated the behavior .7. 5.

In thermochromatography experiments three different processes can be distinguished. Due their very similar energies. These are: 1. Due to their high volatility the oxide hydroxides appear to be especially interesting for an on-line gas chromatographic study of Bh. a small fraction of Re remains as non-volatile compound at the starting position (peak A in Figure 17). This behavior is observed if the employed quartz columns are pretreated in excess of 1000 °C with and with or as reactive component of the carrier gas. This behavior is observed if the employed quartz columns are pretreated in excess of 1000 °C with and with or as reactive component of the carrier gas. The rapid formation of the rhenium trioxide and a gas governed by mobile adsorption chromatographic transport of processes to deposition temperatures of about 500 °C (deposition peak B in Figure 17).260 The Chemistry of Superheavy Elements of long-lived Re nuclides in thermochromatographic systems as well as the one of short-lived Re nuclides in on-line isothermal chromatography. The results of these studies [53] are summarized in Figure 17 and can be described as follows: Thermochromatography of oxides and oxide hydroxides. A high volatility of the investigated compound gives rise to high separation factors from less volatile by-products. The latter leads to a reversible formation of more volatile via a surface catalyzed reaction and thus. 2. C. This behavior is observed if the employed quartz columns are pretreated in excess of and with as reactive component of the carrier gas. 3. they usually hamper a sensitive detection of transactinides. such as heavy actinides. and D in Figure 17. through the intermediate to a transport of to lower adsorption temperatures (deposition peak C in Figure 17). reflected in the deposition peaks B. Pb and Bi nuclides. but also from Po. The formation of the rhenium trioxide and a consecutive by mobile adsorption and a superimposed transport transport of reaction. depending on the pretreatment of the column surface and the oxidation potential of the carrier gas. The rapid formation of the perrhenic acid and a gas chromatographic transport of the rather volatile governed by mobile adsorption processes to relatively low deposition temperatures of less than 100 °C (deposition peak D in Figure 17). . 1000 °C with Also.

The much more volatile was not the volatile species as observed at the given experimental conditions. In order to obtain the volatile (containing 500 ppm saturated with at room 100 ml/min temperature were added as reactive components. Gas-Phase Chemistry 261 Isothermal chromatography of oxides and oxide hydroxides. Section 4. The deduced kJ/mol was in good agreement with (evaluated from peak B shown in Figure 17) measured in thermochromatography experiments and this value identified [53]. A kinetic hindrance of the formation of was excluded. where the The reaction products were oxidized and the aerosols converted to yield of volatile Re oxides was measured as a function of the temperature in the adjoining isothermal section of the column. The nuclide with its branch is ideally suited to model the behavior of its heavier group-7 homologue Bh and was produced in the fusion reaction Transfer reaction products such as served as model elements for the behavior of heavy and actinides. The resulting temperature vs.7. see Chapter 4. high yields of a volatile Re compound were only observed at temperatures of 900 K and above. Unfortunately. Based on thermochromatographic studies on-line methods for the gas chromatographic isolation of volatile group-7 oxides or oxide hydroxides were investigated using the OLGA technique [53]. yield curve is shown in Figure 18.3. . The carbon aerosols were stopped on a quartz wool plug in the reaction oven at 1373 K. Reaction products were transported attached to carbon aerosol particles in He from the target site to the OLGA set-up. since also much longer-lived Re nuclides were not observed after chemical separation.

separation factors of were deduced. This approach had already been successful in studies of volatile Db and Sg oxychlorides. an on-line isolation of very volatile group-7 oxide hydroxides was not accomplished. the oxide system provided an excellent separation from lanthanides [53] and actinides [50. chlorides and oxychlorides were investigated as potential candidate compounds for an on­ line gas chemical isolation of Bh [54]. a number of different chloride/oxychloride species exist within group 7 and thus the chemical speciation of the formed compounds appears to be complicated. were found to be similarly volatile as In conclusion.2 Chlorides and oxychlorides Since the oxide and the oxide hydroxide systems are not well suited to rapidly isolate single atoms of group-7 elements [53]. Nevertheless.1.262 The Chemistry of Superheavy Elements Po and Bi as possibly interfering contaminants were also investigated under the same experimental conditions and. 5. as well as the oxychlorides and . as shown in Figure 18. For Re the pure chlorides and are known. 51]. However. The isolation of less volatile trioxides appeared not to be promising due to the interference of Po and Bi by-products hampering the unambiguous identification of Bh nuclides after chemical isolation. see Sections 3 and 4 of this chapter.

Variation of the carrier gas mixture He (Vol. Eichler et al. . the gas was further investigated in on-line chemical system isothermal chromatography using short-lived Tc and Re nuclides. (Vol. The observed properties of group-7 trioxychlorides oxychlorides in thermochromatography experiments appeared quite promising for a first chemical identification of Bh.7. The deposition zone of Tc was observed at a lower temperature as the one for Re and coincided with the which was formed in the reaction of HCl and condensation zone of at 1400 K in the reaction oven.% 0-80%). Therefore. For this reason. R. and HCl (Vol. Only few thermochromato­ graphic studies of chloride and oxychloride compounds of group-7 elements Tc and Re were known [71-73]. By using an empirical correlation of the measured adsorption enthalpies of trace amounts of a number of chloride and oxychloride species with their macroscopic boiling point identified the formed volatile species quite clearly as the M=Tc. Therefore. only one single deposition zone for Tc and Re was observed at rather low deposition temperatures. [54] reinvestigated the thermochromatographic behavior of Tc and Re in quartz columns in the gas chemical system using trace amounts of the nuclides and obtained from a thin fission source and produced from proton irradiations of Due to the large variety of chloride and oxychloride compounds of group-7 elements Tc and Re many different deposition zones were expected in thermochromatography experiments. Re). Surprisingly. see Figure 19. only an upper limit of the adsorption enthalpy of the Tc compound was established.% 0-60). Gas-Phase Chemistry 263 Thermochromatography of chlorides and of oxychlorides. indicating the formation of a very volatile compound.% 10-100) did not yield any other volatile compound.

were and serving as model elements for the lighter transactinides Rf and Db. As shown in Figure 20. the gas chemical system was shown to fulfill all requirements for a first successful chemical identification of Bh [54]. serving as models for heavy actinides. . This interesting property allowed a distinction between a "Tc-like" and a "Re-like" behavior in a first experiment with Bh. Ancillary experiments with the and were conducted to investigate the separation of volatile Tc and Re trioxychlorides from Po and Bi contaminants. this approach did not work Obviously. Thus. At the column exit the separated volatile molecules were adsorbed on the surface of CsCl aerosol particles of a second gas-jet ("reclustering") and were rapidly transported to a detection system. such as significantly improved the yield. Yields of 80% were observed compared to the activity of entering the OLGA III set-up.264 The Chemistry of Superheavy Elements Isothermal chromatography of chlorides and oxychloride. However. the adsorption enthalpy of for the more volatile on a CsCl surface was too low to allow an efficient reclustering. the separation of Tc and Re is excellent. As in Studies of group-7 oxides and oxide hydroxides short-lived were used. were separated at isothermal temperatures up to 470 K with separation factors of An average overall process time of about 3 s was evaluated for Re. As reactive gases HCl and were added to the He/C-aerosol gas-jet shortly before the reaction oven. Nuclear reaction products were oxidized and chlorinated together with the carbon aerosols. trioxychlorides from the less volatile BiOCl or Separation factors from lanthanides. Using aerosols with a reducing surface. see below. Short-lived and were obtained from a fission source.

2 GAS CHEMICAL STUDIES OF BOHRIUM 265 5.2 and 4. were transported to the on-line chromatography set-up OLGA.A. In the reaction oven of OLGA. 3. A spectrum of all from all runs (93 MeV and 96 MeV bombarding energy) and all detectors revealed that a small portion of heavy actinide isotopes had passed through the gas chromatographic column. The water content of the gas mixture was kept below 100 ppm in order to form only the trioxide species. No SF tracks were observed in a temperature range from 800 °C down 20 °C. which passed through the second part of the column with a negative temperature gradient ranging from 1050 °C down to 500 °C at the exit of the column.2. This negative result was interpreted that either the half-lives of the produced Bh nuclides were shorter than 2 s or that the production cross sections were lower than 100 pb [50]. were deposited on thin Ni catcher foils that were coated with Ta.2.2. attached to the surface of KCl aerosols.2. Eichler et al. [52]. Db and Sg. Reaction products recoiling from the target were thermalized in He containing 20% and. in a different attempt M. [53] showed that the rapid formation of a volatile oxide hydroxide is hindered. but that the decontamination factor was better than Even though a couple of were registered . [51] bombarded a with ions to produce the isotopes and at the 88-Inch Cyclotron of the Lawrence Berkeley National Laboratory (LBNL). while the nuclide (produced from an admixture of to the target material) was adsorbed at around 200 °C. Moist air with a water vapor pressure of 600 Pa at a flow rate of 0. In the last 3 experiments an optimum purification from actinides was achieved.75 1/min passed behind a thick target that was irradiated with ions.7. Eight experiments were conducted with varying conditions concerning the operation of the thermochromatographic column. Wilk et al. they searched for latent tracks in thermochromatographic columns imprinted by the stopping of a fission fragment from the decay of a spontaneously fissioning isotope of Bh. Zvara and co-workers already in 1984 [50]. Schädel et al. the KC1 aerosols were stopped and were destroyed on a quartz wool plug. respectively. the studies by R. Gas-Phase Chemistry 5. Volatile oxides.2 On-line gas chromatography of oxides target Later. As in earlier experiments with Rf. The catcher foils were mounted on the circumference of a rotating wheel and stepped periodically between pairs of surface barrier detectors to register and SF decays. 5. as determined in test experiments with Re. Even though the reached cross section limits are very close to the cross sections measured later by P.1. see above Sections 2.1 Thermochromatography of oxides and/or oxide hydroxides A first attempt to chemically identify element 107 as eka-rhenium was conducted by I. kept at 1050 °C.

000 samples were measured.3 Isothermal chromatography of oxychlorides In an experiment at the PSI Philips cyclotron. 1.2 MeV none of these could be conclusively attributed to the decay of a Bh isotope. Assuming a transport time of about 1 s and a half-life of the produced Bh isotopes of more than 2 s. cross section limits of about 3 to 10 nb were reached (95% confidence level). The target was irradiated for about per second at a beam four weeks with typically particles of energy in the middle of the target of 119±1 MeV. the first successful chemical isolation and identification of Bh was accomplished [55].2. 150°C. and a statistical treatment of this background. The properties of the observed decay chains are shown in Figure 21. These upper limits were larger than the calculated production cross sections by more than one order of magnitude. A total of 6 genetically linked decay chains attributed to the decay of were observed. producing 17-s in the reaction was simultaneously produced in the reaction and served as a yield monitor for the chemical separation process. As outlined by the authors. Measurements were performed at isothermal temperatures of 180°C. At each isothermal temperature a beam integral of particles was accumulated. . the experiment clearly failed to chemically identify Bh.1 out of 2 observed decay chains.266 The Chemistry of Superheavy Elements with energies between 8. A target of 670 covered with a 100 layer of was prepared at LBNL on a thin Be foil. Nuclear reaction products recoiling from the target were attached to carbon aerosol clusters and were transported with the carrier gas flow through a capillary to the modified OLGA III set-up. After chemical separation final products mixture of HCl and were attached to CsCl aerosols and were transported to the rotating wheel and SF decays were registered detection system ROMA where event by event in almost geometry. Due to a small contamination with Po and Bi nuclides.4 and 9. 5. As reactive gases a was added. four at an isothermal temperature of 180°C. and 75°C. No genetically linked decay chains were observed.3 of the 4 decay chains observed at 180°C had to be attributed to accidental correlations unrelated to the decay of At 150°C this correction was only 0. Throughout the experiment close to 180. two at 150°C and none at 75°C.

which was not suitable to recluster the very volatile [54]. . were and (68% confidence interval). for a relatively high yield of 80% was observed at 75°C as compared with the yield at 180°C isothermal temperature. The relative yields of the compounds and (most likely) as a function of isothermal temperature are shown in Figure 22. is less volatile than The fact that was identified after chemical separation already excludes a "Tc-like" behavior of Bh. the The probability that sequence in volatility is is equally or more volatile than is less than 10%. This indicates that which was not observed at 75°C. Gas-Phase Chemistry 267 Interestingly. The deduced enthalpies of adsorption on the column surface kJ/mol. Therefore. since CsCl was used as the recluster aerosol material.7.

also classical extrapolations down the groups of the Periodic Table making use of empirical correlations of thermochemical properties predict to be more stable and less volatile than or [75]. Section 2. Part II. As in the case of Sg oxychlorides the experimentally determined can be used to estimate a macroscopic sublimation enthalpy of see Chapter 6. [74]. . It was therefore possible to directly estimate from only a few investigated molecules.3. using an empirical linear correlation function.268 The Chemistry of Superheavy Elements This sequence in volatility agrees well with predictions from fully relativistic density-functional calculations for group-7 oxychlorides that have been performed by V. Pershina et al. The results of these calculations showed that the electronic structure of is very similar to that of or Increasing dipole moments and electric dipole polarizabilities in the group suggest a decreasing volatility in the sequence However.

which is known to form tetrahedral Ru and Os is quite similar. Darmstadt.1 VOLATILE COMPOUNDS OF GROUP-8 ELEMENTS Group-8 elements Fe.5 ms. Only in 1996. element 108) has. Ru and Os are the elements with the highest maximum valency within their periods and the only elements which can form an 8+ oxidation state (with the exception of [80]). A somewhat larger production cross section of about 7 pb could be expected for the direct production of in the reaction [78]. Ru and Os are known to exist in a large number of oxidation states: Fe is known in all states from -2 through +6. 6. While the chemistry of Xe. very likely [79]. However.7. as a presumed member of group 8 of the Periodic Table and thus a homologue of Fe. the much with a half-life of the order of about 10 s was longer-lived isotope chain of the nuclide [77]. very similar to The discovery of Hs was reported in 1984 [76] with the identification of the nuclide with a half-life of only 1. Element 108) The experimental chemical investigation and characterization of the next heavier transactinide element Hassium (Hs. constituted a daunting task even though from the very beginning the selection of a volatile compound was absolutely clear. The reason is the existence of the lanthanide series which is inserted in the sixth period of the Periodic Table. Gas-Phase Chemistry 269 6. and proved that Hs behaves like a typical member of group 8 and forms volatile Hs-oxide molecules. the state of the art techniques. that have successfully been applied to chemically identify Bh had to be improved by at least one order of magnitude! This goal was indeed accomplished by introducing novel techniques for irradiation. The most important volatile compounds of Ru and Os are the tetroxides (M=Ru. Ru. investigations of the chemical properties for a future Hs chemistry experiment concentrated on Ru and Os. Fe behaves differently. should form stable and at the same time very volatile molecules. . the observed in the production cross section of only about 1 pb for the reaction 112 was discouragingly small. Hassium. for some years. Hassium (Hs. Ru in the states -2 through +8 (with the exception of +1) and Os in all states from -2 through +8 explaining the large variety of compounds. far too short for all of the currently available chemical separator systems. separation and detection. The successful Hs chemistry experiment was conducted in the spring of 2001 again in the framework of an international collaboration at the Gesellschaft für Schwerionenforschung. and Os. Therefore. Thus.

early considerations [81. The columns were filled with quartz powder Os was completely volatilized and adsorbed at -40 °C. This peak was therefore attributed to Ru transported by a transport reaction of the type However.82] and experimental developments [83-96] for a first Hs chemistry exclusively concentrated on the tetroxides. 96]. Quite naturally. The transport of Ru appears to occur by chemical transport reactions where the chemical species change during the chromatographic process. with an adsorption enthalpy of . but not observed in [86]. but experimentally difficult to handle. Tc.1 Thermochromatography of oxides The volatilization and deposition of carrier-free radionuclides of the elements Re. The location of the deposition peak at higher temperatures varied over a wide range in different experiments and disappeared completely in experiments lasting more than one hour. This strategy is justified. and Ru in a thermochromatography column were studied using air as a carrier gas [83]. [92] using as carrier gas. Os. Ir. The deduced enthalpy of adsorption on the quartz surface was kJ/mol. The fluorides and oxyfluorides are of importance. In experiments by Ch. two deposition peaks were observed.1. Düllmann et al. Ru was deposited at much higher temperatures around 400 °C and identified as Later. 85. since classical extrapolations [97] as well as fully relativistic density functional theory calculations on the group-8 tetroxides [98] predict the existence of a volatile and very stable 6. The second peak at lower deposition temperatures was attributed to transported by mobile adsorption. First indications that also Ru can be volatilized in the form of were obtained in [85]. see Figure 23. does not exist in macroscopic quantities. Mo. There also exist a number of volatile Ru and Os halides and oxyhalides. The transport of Ru oxides in a temperature gradient tube appears to be more complicated.270 The Chemistry of Superheavy Elements Os). in different on­ line TC experiments consistently values for between 39 and 41 kJ/mol were determined [79.

Gas-Phase Chemistry 271 6.60%.2 Isothermal chromatography of oxides In order to directly detect the nuclear decay of Hs isotopes in a future experiment. At the exit. First. by installing an oven as closely as possible to the recoil were obtained simply by using a mixture of chamber high yields of as carrier gas. The addition of aerosol particles was not necessary. The experiments by A. the stream was mixed with a stream of Ar loaded with Pb aerosols on which the was adsorbed and reduced to non-volatile The Pb aerosols were collected on a stepwise moving tape by impaction and transported in front of decay of the isolated Os nuclides. The transported with minimal losses by the carrier gas at room temperature through an open quartz chromatography column. Yakushev et al. 6 PIPS detectors to register the The overall yield (not including the detection efficiency) was measured to be 50 . [94] with demonstrated several important aspects of a future Hs experiment. but the chemical yield of short-lived Os nuclides could substantially be molecules were improved by heating the attached oven [95]. was already formed "in-situ" in the recoil chamber [93].1. Indeed. test experiments with short-lived.7. . emitting Os isotopes were conducted.

5 kJ/mol was determined. [97] measured a yield see Figure 24. all gases had to be carefully dried.96] = 38. But the gain of at least one order of magnitude was not yet accomplished. [93] also employed the in-situ production of Ru.272 The Chemistry of Superheavy Elements Experiments by A. In agreement with thermochromatography experiments [79. The decontamination from interfering elements i.and Os tetroxides in oxygen containing carrier gases. Glass fiber filters soaked with 1 M NaOH yielded the best results. Düllmann et al. were synthesized in-situ in the recoil chamber and transported Volatile by the carrier gas to a quartz chromatography column that could be operated between ambient temperature and -80 °C. In order to prevent the build-up of ice in the column. Po was determined to be The yield of the IVO technique was of the order of 50% and therefore about a factor of 3 more efficient than the OLGA system used in experiments with Bh. but were aimed at studies of the adsorption properties of volatile tetroxides on different surfaces at room temperature. but also freshly prepared Na surfaces provided good adsorption of Using a similar set-up as in [94] Ch. isothermal temperature breakthrough curve of This set-up was named In-situ Volatilization and On-line Detection (IVO). At the exit of the column volatile molecules were adsorbed on the surface of Pb aerosols and transported to the ROMA counting system.e. vs. von Zweidorf et al. .0±1.85.

and Po. [90]. A set-up called On-line Separation and Condensation AppaRatus (OSCAR) was installed at the LBNL 88-Inch Cyclotron. In model experiments with Os. i. Ra. Nuclear reaction products were collected with a KCl aerosol gas-jet and were transported from the target chamber to the OSCAR set-up where was added. Non volatile reaction products were retained on the quartz wool plug whereas the volatile tetroxides were swept by the carrier gas flow to a condensation chamber. Recoiling atoms were thermalized in a mixture of Ar + 2% and were continuously swept from the target chamber through a Teflon capillary to a quartz column kept at 1000-1100 °C and filled with CaO to retain non­ volatile nuclear reaction products. In a second experiment.J. using the reaction B. The decontamination from actinides was excellent as well as that from Po Nevertheless. where they were deposited on a Ag disk. quantitatively on Lavsan (polyethylenphtalat) fission track detectors covered with of Pb. [88] searched also for short-lived emitting isotopes of Hs. Atoms recoiling from the target were stopped in air and transported to a thermochromatography column. At the opposite side an annular Lavsan track detector (also coated with of Pb) was located for registering fission fragments. Fr. Dougan et al. No SF decays were registered resulting in a production cross section limit of 10 pb for nuclides with half-lives longer than 150 ms.2 EARLY ATTEMPTS TO CHEMICALLY IDENTIFY HASSIUM A first unsuccessful attempt to chemically identify Hs as volatile was was reported by B. Gas-Phase Chemistry 273 6. which was cooled with liquid An annular Si . where the purification was adsorbed from actinides took place on a hot quartz wool filter.5 MeV and no SF events were registered and an upper limit of 100 pb for the production cross sections of nuclides with half-lives in the range between 50 ms and 12 h and of 50 pb for spontaneously fissioning nuclides was established. [88] from Dubna. The whole counting device was placed inside a shielding of Cd and paraffin in order to decrease the was efficiently absorbed background. on the Pb surfaces. These were rapidly isolated as volatile tetroxides to detect their SF decay. Volatile species were then transported through a Teflon capillary and blown onto the surface of a Si detector covered with 50 of Pb. Zhuikov et al.e. A similar experiment was reported by R. Zhuikov et al. actinides.7. The reaction employed to produce short-lived isotopes of element 110 and their Hs daughter nuclides. no (separation factor particles in the energy range above 8. The aerosol particles were destroyed on a hot quartz wool plug and the formation of tetroxides occurred at a temperature of 650°C.

. The overall efficiency of the set-up (including detection of a 3 member chain) amounted to 30 . The required gain in sensitivity of one order of magnitude compared to the OLGA set-up used in experiments with Bh was thus accomplished. the most promising approach to synthesize relatively long-lived Hs isotopes appeared to be the reaction Second. Section 2.. the "in-situ" production [95] allowed for highest possible chemical yields of group-8 tetroxides. Dougan et al. the rate of production could be increased by using an intense beam impinging on rotating targets.1. Fourth. Zhuikov et al.. Third. . Kirbach et al.7 and 11 MeV were observed and an upper limit for the production cross section of 1 nb was derived. Such a technically very challenging irradiation set-up was constructed and put into operation by M. The only problem of the thermochromatographic technique so far was the unambiguous identification of the decaying nuclide. This problem has been solved by U. The experiments by B. see Chapter 4. [90] clearly demonstrated that the chemical selectivity would have been sufficient for a first chemical identification of Hs. With the rotating target wheel. Schädel et al. no between 8. [88] and R.3.J. 6.50%. in order to compare with those of its lighter homologues of group 8. However.274 The Chemistry of Superheavy Elements surface barrier detector registered and SF decays of nuclides adsorbed on the disk surface. The OSCAR set-up was used to search for decaying the expected EC decay daughter of (estimated ECdecay half-life: 25 m). First. the volatility of thermochromatography is the method of choice since the position of every detected atom contributes chemical information. assuming a production cross section of 7 pb. However. In the actual Hs experiment an improved version namely the Cryo On-Line Detector (COLD) was used. produced in the reaction. [96] who have built a rectangular thermochromatography column consisting of PIN diodes. see Chapter 4. resulting in the expected detection of about one decay chain per day of experiment.3 ON-LINE THERMOCHROMATOGRAPHY OF HASSIUM In order to reach the required sensitivity and to obtain at the same time meaningful chemical information about Hs and its compounds different experimental developments had to be combined. Section 4. synthesis of about 3 atoms of per day could be expected.4. the overall efficiency and the longtime stability of the experiments to reach the required sensitivity were not sufficient.

valid data was collected during 64. see Figure 25.7. No additional three-member . 99]. During the experiment. seven correlated decay chains were detected. During this time beam particles passed through the target. where the temperature was sufficiently low to partly adsorb Rn. and their decay products accumulated in the last three detectors. While from and its decay daughter were deposited mainly in the first two detectors.2 h. Only originating and their decay products were identified. Gas-Phase Chemistry 275 In an experiment to produce Hs isotopes conducted in May of 2001 at the GSI. while two other decay chains were attributed to the decay of The last two decay chains were incomplete and a definite assignment to or could not be made. All decay chains were observed in detectors 2 through 4 and were assigned to the decay of either or the yet unknown The characteristics of three decay chains agreed well with literature data on and its daughter nuclides [77.

As in experiments with lighter transactinide elements the Monte Carlo model of I. . was used to evaluate the adsorption enthalpy of and on the silicon nitride detector surface. The longitudinal distribution of the 7 decay chains originating from Hs is depicted in Figure 26. The background count-rate of with energies between 8. respectively. that describes the microscopic migration of a molecule in a gas chromatographic column. being of random origin. In addition. leading to very low probabilities of and for any of the first five chains and any of the last two chains.0 and 9. four fission fragments with energies >50 MeV that were not correlated with a preceding were registered in detectors 2 through 4.276 The Chemistry of Superheavy Elements decay chains with a total length of s were registered in detectors 2 to 10. The distribution of measured before and after the experiment showed a maximum in detector 6 at a deposition temperature of -82 ± 7 °C.5MeV was about per detector. The modeled distributions with = 46 ± 2 kJ/mol (68% confidence interval) and are shown as solid lines in Figure 26. The maximum of the Hs distribution was found at a temperature of -44 ± 6 °C. Zvara [18].

all other Hs oxides are expected to be much less volatile and unable to reach the detector system. While early attempts to chemically identify superheavy elements did not reach the required sensitivity to investigate elements that can be produced only at the picobarn level. Extrapolations by B. Gas-Phase Chemistry 277 The higher deposition temperature of about 40 °C and the thus about 7 kJ/mol higher adsorption enthalpy seems to indicate a slightly lower compared to its lighter homologue This volatility of experimental result was somewhat unexpected since according to both. see Chapter 6.2. was classical extrapolations and relativistic molecular calculations.1 VOLATILITY OF GROUP-12 TO GROUP-18 ELEMENTS AND COMPOUNDS Due to the expected high volatility of elements with atomic numbers 112 to 118 in the elemental state [104]. the focus of chemists has shifted to the chemical exploration of superheavy elements. the jump to elements 112 and 114 appears quite natural. [106] point to Pd or Cu as ideal surfaces for the adsorption of superheavy elements. see Chapter 8. see also Chapters 2 and 6. An interesting question is.g. if e. Eichler et al. or if they retain some metallic character and are thus adsorbed quite well on certain metal surfaces. gas phase chemical studies will play an important role in investigating the chemical properties of the newly discovered superheavy elements. Part II. Keeping in mind that there are currently no long-lived isotopes known of elements 109 through 111 (except for the daughter nuclei of and that there are also no obvious choices for their chemical investigation. Section 3. rather than continuing with Mt. two recent attempts to characterize element 112 have provided very interesting results. Future studies with spherical superheavy elements With the reported synthesis of long-lived isotopes of elements 112 and 114 in induced reactions on and targets [101-103]. .7. respectively. element 110 and so on. elements 112 and 114 are indeed relatively inert gases (similar to a noble gas) [105] due to closed and shells. 7. by analogy with the known properties of the Os oxides. Nevertheless. 7. the high volatility of predicted to be about as volatile as the Hs oxide species clearly suggests that it is since. The observed formation of a volatile Hs oxide (very likely provides strong experimental evidence that Hs behaves chemically as an ordinary member of group 8 of the Periodic Table.

and Pd surfaces at room temperature. Hg adsorbed quantitatively on Au. K. Yakushev et al.278 The Chemistry of Superheavy Elements Besides the elemental state. Since isotopes of the group 14 to 16 elements Pb and Po severely interfered with the detection of transactinide halides and oxyhalides in the case of Rf. due to the high mentioned isotopes a very clean separation between Pb. N. However. the formation of volatile halides (or oxyhalides) of elements 114. The chemical yield for the simultaneously produced was 80%. Bi. methyl.and ethyl compounds of elements 113 through 117. Eight detector chambers (6 Au and 2 Pd) were connected in series by tubing. Trautmann et al. and Sg. [108] showed. as in the successful proved experimentally not feasible.2 ISOTHERMAL CHROMATOGRAPHY OF ELEMENT 112 A first attempt to chemically identify one of the recently found long-lived isotope of element 112. short-lived Hg isotopes were produced from a small admixture of Nd to the target material. Bächmann et al. However. Db. and 116 energies of the above can be expected. [107] extrapolated the boiling points of hydrides. detector chambers containing a pair of Au or Pd coated PIPS detectors were constructed. The detector chambers were positioned inside an assembly of 84 filled neutron detectors (in a polyethylen moderator) in order to simultaneously detect neutrons accompanying spontaneous fission events. In an experiment conducted in January of 2000 a total beam dose of ions was accumulated. also volatile compounds of superheavy elements have been considered. 115. Adsorption of Hg nuclides on silicon detectors. [109] in Dubna. Pt. If element 112 behaved chemically like Hg and all efficiencies measured for Hg were also . As little as 1 of Au or Pd surface was sufficient to adsorb Hg atoms nearly quantitatively from a stream of 1 1/min He. 7. Therefore. and Po and the transactinide elements must be accomplished in order to study heavy transactinide halides (or oxyhalides). see Figure 27. probably as diethylpolonium. The nuclide was produced by bombarding a target with ions. namely in the elemental state was made by A. since Hg was experiment with adsorbed on quartz surfaces only at temperatures of -150 °C and below. In test experiments short-lived Hg isotopes could be isolated in the elemental form from other reaction products and were transported in He quantitatively through a 30 m long capillary at room temperature. Simultaneously. that short-lived was volatilized using ethyl radicals.

the majority of the SF events were attributed to the decay of a nuclide of element 112. Again zero SF events were registered on the Au and Pd coated PIPS detectors. while only one background count was expected. no unambiguous answer as to the chemical and physical properties of element 112 was obtained. and SF Therefore. no SF events were observed. In a next experiment. . Therefore. the question whether element 112 remained in the gas phase and passed over the Au and Pd surfaces was addressed [110]. 8 SF events accompanied by neutrons were registered in the ionization chamber. Gas-Phase Chemistry 279 valid for element 112. However. since there are no other known volatile nuclides decaying by SF. However.7. detection of events could be expected measured in assuming the cross section value for the production of [101]. Therefore. A total beam dose of ions was accumulated. a special ionization chamber to measure fragments of nuclei remaining in the gas was added at the exit of the Au or Pd coated PIPS detector array. confirming the result of the first experiment.

The temperature in the gradient should start at room temperature and reach down to the adsorption temperature of Rn. Obviously. the enthalpy of adsorption of element 112 on Au surfaces has to be measured experimentally. which should be still above the temperature of liquid .280 The Chemistry of Superheavy Elements From this experiment it appears that the interaction of element 112 with an Au or Pd surface is much weaker than for Hg. in a next step. This can be done with a cryo thermochromatography detector containing Au coated detectors. The obtained enthalpies of adsorption were and (element 112) Such a vastly different chemical behavior as in the present case of element 112 compared to its lighter homologue Hg has not been observed for any of the lighter transactinides so far and might reflect the predicted inertness and enhanced volatility due to relativistic effects.

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7. Gas-Phase Chemistry


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The Chemistry of Superheavy Elements

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The Chemistry of Superheavy Elements


239, 240, 244, 251, Adsorption 253, 256, 257, 260, 263, 264, 267, 268, 270, 271, 272, 276, 277, 280 Dissociative 253, 256, 257 253, 256, 257 Reversible Substitutive 239 Bismuth (Bi, Z=83) 241, 260, 262, 264, 266, 278 Bohrium(Bh, Z=107) 258, 259, 260, 261, 262, 263, 264, 265, 266, 267, 269, 272, 274 Boiling point 248, 251, 263, 278
273 Cadmium (Cd, Z=48) Carbonyls 251, 253 Chemical separation 237, 241,
251, 253, 255, 259, 260, 261,
262, 264, 266, 267, 269, 273,
275, 278
257, 262, 264
241, 242, 243,
244, 245, 248, 250, 252, 254,
256, 257, 260, 261, 262, 263,
264, 265, 266, 270, 272, 273,
274, 284
Gas-phase 251
Liquid-phase 237
Selectivity 274
Single atom chemistry
241, 262 Speciation 262 Chemical transport reaction 242, 243, 253, 256, 260, 266, 270 Chromium (Cr, Z=24) 251, 253, 259 COLD 274, 275 Copper (Cu, Z=29) 277 Cryo thermochromatography 274, 275

251, 255, 257, Decay chain 259, 266, 267, 275, 276 240 d-element behavior 240, Deposition temperature 243, 247, 260, 263, 270, 276, 277 Detection 237, 241, 248, 254, 257, 260, 264, 266, 269, 271, 274, 278,279 Detection system 274, 275 COLD ROMA 255, 257, 266, 272 Detector 239,253 Mica fission track PIN diode 274 PIPS 271, 278, 279 Dubnium(Db, Z=105) 245, 247, 248, 249, 250, 252, 253, 262, 264, 265, 278 240, 273, 277 Element 110 277 Element 111 Element 112 241, 277, 278, 279, 280 Element 113 278, 281, 282, 283 Element 114 238, 277, 278 278, 284 Element 115 278 Element 116 Element 117 278 Element 118 241, 277 Enthalpy of adsorption 251, 263, 264, 268, 270, 276, 277 Enthalpy of sublimation 238, 252, 256, 268 Extrapolation of chemical properties 242, 244, 245, 249, 250, 268, 270, 277

7. Gas-Phase Chemistry f-element behavior Francium (Fr, Z=87) 241 273 HITGAS


256, 257

Gadolinium(Gd, Z=64) 241 Gas-jet 257, 264, 273 242, 243, 257, 261, Aerosol 264, 266, 267, 271, 273 Capillary 255, 266, 273, 278 Carbon aerosol 242, 254, 261, 264, 266 243, 265, 273 KC1 aerosol aerosol 242, 252, 257 Gold (Au, Z=79) 278, 279, 280 Ground state configurations 238, 245 Group 4 elements 238, 239, 243, 250 Group 5 elements 245, 250 Group 6 elements 238, 251, 253, 254, 255, 256, 257, 258, 259 Group 7 elements 258, 259, 261, 262, 263, 264, 268 Group 8 elements 238, 269, 270, 274, 275, 277 Hafnium (Hf, Z=72) 238, 239, 240, 241, 242, 243, 244, 245, 247 Halides 238, 239, 241, 244, 245,
246, 250, 251, 253, 259, 270,
238, 241, 243, 244, 245, 247, 249, 250 Chlorides 238, 239, 240, 241, 242, 243, 244, 245, 247, 249, 250, 252, 253, 262, 263, 264 Fluorides 238, 239, 270 Iodides 238 241, 242, Halogenating agents 243, 244, 247, 248, 249, 251, 253, 255, 263, 264, 266 Hassium (Hs, Z=108) 269, 271, 273, 274, 275, 276, 277, 285 HEVI 241, 242, 243, 244, 245

In-situ 241, 271, 272, 274 Iron (Fe, Z=26) 259, 269 Isothermal gas chromatography 237, 239, 241, 242, 244, 246, 248, 251, 253, 254, 255, 256, 257, 258, 260, 261, 262, 263, 264, 266, 267, 268, 272 IVO 272 Kineamtic separator 279

Lead (Pb, Z=82) 238, 241, 260, 271, 272, 273, 278 Manganese (Mn, Z=25) 258, 259 277 Meitnerium(Mt,Z=109) Mercury (Hg, Z=80) 239, 278, 280 Molybdenum (Mo, Z=42) 242,

250, 251, 252, 253, 255, 256,
257, 270 Monte Carlo model 255, 257, 276 242, 244,

Neodymium (Nd, Z=60) 278 Niobium (Nb, Z=41) 246, 247, 248, 249, 250 Nuclides

255, 258 263 271 264 244 255, 258 261, 264 254 263 278 278 278 278 278


The Chemistry of Superheavy Elements

Nuclides cont.
278 278 264 262, 264 241 248 241 248 267 240 247 241, 243, 244, 275 248, 249 257, 275 267 250, 253 265 269 251,254, 255, 257, 275 258, 265 251, 254, 256, 257, 275 258, 266, 267 273 269, 274, 275 275 274 274 269 277 278, 279 277 278, 279 247

Oxyhalides 238, 239, 245, 246, 250, 251, 253, 259, 270 Oxybromides 238, 249, 250 Oxychlorides 238, 239, 242, 243, 247, 248, 250, 251, 252, 253, 254, 255, 258, 259, 262, 263, 264, 268 Palladium (Pd, Z=46) 277, 278, 279, 280
p-element behavior
238, 241 Platinum (Pt, Z=78) 278 Polonium (Po, Z=84) 241, 257, 260, 262, 264, 266, 272, 273, 278 Production rate 250 Projectile 241, 242, 248, 249, 253 261 239, 247, 254, 256, 257, 258, 265, 266, 273, 274 269, 274 273 277, 278, 279 Protactinium (Pa, Z=91) 265 Radium (Ra, Z=88) 273 Radon (Rn, Z=86) 238, 245, 275, 280 Recoil catcher foil 265 Relative yield. 246, 255, 257, 267, 268 Relativistic effects 242, 245, 268, 270, 277, 280 Retention temperature 238, 242, 244
Rhenium (Re, Z=45)
258, 259, 260, 261, 262, 263, 264, 265, 270 ROMA 255, 257, 266, 272 Ruthenium (Ru, Z=44) 269, 270, 271, 272

OLGA 241, 242, 243, 244, 245, 250, 254, 261, 264, 265, 266, 272, 274 OSCAR 273 Osmium (Os, Z=76) 269, 270, 271, 272, 273, 277 246, 251, 252, Oxidation state
259, 269

246. 253. 278. 253. 240. 274 Target set-up Beryllium window 266 Technetium (Tc. 265. 251. Thermochromatography 243. 275 . 241. 254. 252. 240. 274. 238. 280 Tungsten (W. Gas-Phase Chemistry 289 Rutherfordium (Rf. 244. Z= 106) 250. 254. 270 Tetroxides 238 240. 279 Synthesis 258. 251. 255. 253. 260.250. 272. 275. 253. 257. Z=74) 250. 277 Tantalum (Ta. 259. Z=104) 237. 269. 239. 258. 273 258. 273. 249. 273. 248. 263. 278 248.255. 254. 253. 254. 264. 257. 252. 280 Zirkonium (Zr. 252. 245. 247. 274. 273 277 239 247 277 241. 249. 258. 267. 249. 276. 261. 240. 262. 265. 266 253. 242. Z=73) 245. 258. 265.277. 266.254. 249. 263 Vapor pressure 238. 243. 252. 250. 260.265 Target 241. 256. 263. 261. 256. 278 Spontaneous fission 237. 259. 265. 267. 255. 244. 258. 243. 252. 253. 274. 274. 278 Seaborgium (Sg. 242. 274. 245 238. 264. 257. 241. 265. 277. 256. 274. 268. 239. 247.7. 257. 263. 255. 264. 239. 253. 265 Volatility 238.242. 257. 270. 265. 252. 266. Z=40) 242. 255. 268. 273. 265. 259. Z=43) 258.

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prompt disruption by fission. Swiatecki [3] emphasized the enormous stabilization against fission gained by shell closures. Universität Mainz.J. the next proton shell should be completed at Z=126 in analogy to the known N=126 neutron shell. J. Schädel (ed. D-55128 Mainz. although the discussion in Ref. Introduction In 1955. Together with a new N=184 shell. 291 M. Scharff-Goldhaber [2] mentioned in a discussion of the nuclear shell model. Fritz-Straßmann-Weg 2.). In a study of nuclear masses and deformations. The situation changed in 1966 due to three theoretical papers. Herrmann Institut für Kernchemie. Two years later. © 2003 Kluwer Academic Publishers. Germany 1. Printed in the Netherlands. Wheeler [1] concluded from a courageous extrapolation of nuclear masses and decay half-lives the existence of nuclei twice as heavy as the heaviest known nuclei. Remarkably. 291-318. this shell closure should lead to local region of relative stability. however. G. making them quite stable against spontaneous fission.D.Chapter 8 Historical Reminiscences G. that beyond the well established proton shell at Z=82. hence. The Chemistry of Superheavy Elements. These early speculations remained without impact on contemporary research. .A. Myers and W. Fission barriers even higher than that of uranium could thus occur for nuclei at the next proton shell closure beyond the existing nuclei. lead. This was in sharp contrast to the liquid-drop nuclear model which predicts in the same region vanishing barriers and. [3] focused on Z=126 as the next proton shell closure. W. he called them superheavy nuclei.

thus causing the island-like shape. that 114 should be the next magic proton number. half-lives for should decrease rather uniformly with increasing proton number.292 The Chemistry of Superheavy Elements Z=114 was mentioned as an alternative. Considered were the three major decay modes: spontaneous fission. thus. hence. Spontaneous fission halflives were calculated to peak sharply at the doubly magic nucleus.11] due to the well-known hindrance of spontaneous fission and decay for odd proton numbers. and or electron capture. [6] also derived. perhaps within reach. and. A. with reference to unpublished calculations by H. N=184 revealed an island-like topology as is depicted in Figure 1 [10]. most spectacular at Z=110. Sobiczewski et al. long half-lives for both decay modes were expected to overlap. . In contrast. who presented his results [4] later at the ”Why and How . Meldner. For Z=114. descending by orders of magnitude within short distances in the Z-N plane... the seminal event for superheavy element research. A fantastic perspective was. but only 10 y resulted for In a limited region. opened: an island of superheavy elements located not too far from the then heaviest known element. The nuclei would cross the plane as a diagonal belt. N=184 for which an overall half-life of should result – sufficiently long for the occurrence of superheavy elements in Nature! Additional stability was expected for odd elements such as 111 or 113 [8. Other groups using different theoretical approaches soon agreed. First theoretical estimates [7-10] of decay half-lives around the doubly magic nucleus Z=114. N=184 an enormous spontaneous fission half-life of y was estimated. with some zigzag at the nuclear shell closures.” symposium 1966 [5]. Simultaneously. 103.

Alpha-particle spectra would be less specific.8. no permission by the laboratory director. should also decay into by two particle emissions via as the intermediate. The doubly magic . because the energies predicted for superheavy nuclei fell into the range covered by the natural decay series deriving from uranium . two subsequent should lead via to where the chain should terminate by spontaneous fission with 140 d half-life. Such tracks (Figure 2) are caused by radiation damage of the solid when the energetic fragments are slowed down. detection of fission events in natural samples would give a strong hint. In a detailed theoretical exploration [12] of the Z-N plane around the island. Everybody could feel encouraged to participate. and they can be made visible by chemical etching. no research group. N=184. no proposal to funding agencies – not even a garage. Just an intelligent choice of a natural sample and a corner in the kitchen at home could be sufficient to make an outstanding discovery: new and superheavy elements in Nature. Since spontaneous fission is extremely rare in Nature. The detector would be a simple microscope from school days showing fission fragment tracks accumulated in the sample during geological times. either immediately or after a sequence of other decay steps. the longest-lived nuclide again turned out to be Z=110. half-life 790 y. Due to the topology of the island. superheavy nuclei should decay by spontaneous fission. Historical Reminiscences 293 Such predictions of very long overall half-lives immediately stirred up a gold-rush period of hunting for superheavy elements in natural samples. decaying with half-life by emission to From there. nearly no equipment. no accelerator beam time. Nearly nothing would be needed: little money.

and elaborate chemical treatment would. Several sailors are shown in attempts of crossing the sea of instability. The situation is illustrated in a cartoon. Complete fusion of heavy projectiles with heavy targets – so far very successful in the extension of the Periodic Table by the heaviest elements – was considered the only practical way.294 The Chemistry of Superheavy Elements and thorium. those of the LBL (Lawrence Berkeley Laboratory) at Berkeley/USA were just launching the SuperHILAC linear accelerator (Ge). Already on the way were the crews of the JINR (Joint Institute for Nuclear Research) at Dubna/Soviet Union (now Russia) with the Heavy-ion U-300 Cyclotron (Xe) and of the IPN (Institut de Physique Nucléaire) at Orsay/France with the ALICE cyclotron (Kr). First attempts to produce superheavy nuclei in the laboratory were already undertaken in the late sixtieth. Figure 3. such as uranium or curium. be required to identify the searched components. the UNILAC (U) of the GSI (Gesellschaft für Schwerionenforschung) was still under construction. a large gap had to be bridged between conceivable targets. fighting against hostile forces. . and the island. hence. and at Darmstadt/Germany. These demands had a strong impact on accelerator technology in order to upgrade existing and build novel facilities. However. The then existing heavy-ion accelerators could not provide the required medium-element projectiles in adequate intensities or not at all. which enjoyed the audiences of pertinent conferences in the early seventieth.

A review [21] covering the literature until the end of 1973 was based on already 329 references.8. deviations from straightforward extrapolations within the Periodic Table were also considered [19]. eka-thallium and eka­ lead. Historical Reminiscences 295 Turning to chemistry.15] confirmed this view. element 110 is located below platinum. either for the selection of natural samples. Within a few years. eka-radon. 114 below lead. As a consequence of relativistic effects on the electronic structure. The electron configurations should indeed be analogous to the closest homologues. many aspects of superheavy nuclei and elements were touched. Predictions of properties common to several superheavy elements were carried out for the design of group separations as a first step in chemical search experiments. Consequently.. a series of 6f elements may occur. and status reports [22-27] published from time to time illustrate how the field developed. In a naive continuation of the Table. Examples are the detailed treatments [16] of chemical and physical properties of the 7p elements 113 and 114. However. or the design of chemical identification procedures in synthesis experiments. e. the two s electrons in element 112 and also the two electrons in element 114 could form closed electron shells. Beyond element 121. and eka-mercury and eka-lead could both be chemically inert gases like element 118. Quantum-mechanical calculations of ground-state electronic configurations [14. eka-actinium. But the 5g orbital – the first g orbital at all – may be filled in competition. the crucial question was: where are the superheavy elements located in the Periodic Table and how well do they fit its architecture? The answer had immediate implications for the ongoing “search for” campaigns. as there are two 6s electrons in mercury. Examples are the high volatility of elements 112 to 116 in the metallic state [17]. two 7s valence electrons were predicted for element 112. The chemistry of such elements [14. 112 below mercury.15] would be most exciting. Extrapolations within the respective groups of the Periodic Table should thus be an appropriate approach to predict the chemical behavior of superheavy elements [14]. During this exploratory period continuing until the early eighties the optimistic perspectives of occurrence in Nature and easy synthesis at accelerators were proven in a . a series of 32 superactinide elements [20] may exist in which inner electron shells are filled whereas the configuration of the valence electrons remains unchanged. and 118 becomes the next noble gas below radon. the s. Consequently.and p-orbitals of heavy elements should shrink whereas higher lying orbitals should expand. in analogy to the 5f actinide elements following actinium. or the formation of strong bromide complexes of elements 108 to 116 in solution [18].g.

provided they are produced in the nucleosynthesis. As soon as the stellar explosion ceases. the very short-lived nuclei decay towards the region of by a chain of fast thereby further increasing the atomic number. several neutrons are captured to form very neutron-rich isotopes which decay quickly by transitions to the next heavier element. a half-life of some y for superheavy nuclei would be long enough for their survival until presence. the supernovae. Somewhere at very high atomic . Search for Superheavy Elements in Nature Since the solar system and soon later the Earth’s crust were formed about y ago. Starting at seed nuclei around iron (the theoretical view at that time). These daughter products again and so forth. but shifted to much higher neutron numbers – as is sketched in Figure 4 – with discontinuities at magic neutron numbers. the rcapture neutrons and undergo process path proceeds parallel to the belt of known nuclei to the heaviest elements. which produce free neutrons in tremendous densities and initiate the so-called r-process. 2. This Chapter gives an overview over this pioneering period. In this way.296 The Chemistry of Superheavy Elements trial-and-error approach. Heavy elements beyond iron are created in gigantic stellar explosions. r stands for “rapid”. as is typical for new and attractive research topics.

the r-process is terminated by neutron-induced and fission. But even if the half-lives of superheavy nuclides would not exceed the y level. in natural platinum ores with standard analytical techniques remained negative at a concentration limit of 1 ppb. hence. Another possible source could be the cosmic radiation impinging on Earth whose heavy component may be formed by r-process nucleosynthesis in our galaxy not longer than y ago [33] and may. [34. First searches were reported in 1969 by the Berkeley [10] and the Dubna groups [36]. Other groups [38] found no evidence for spontaneous fission activities in lead and other achieved with the sandwich samples at a lower detection limit of technique. N=184 magic nuclei. attention was drawn [11] to quite a number of earlier reports emitters with energies which do not match with any on natural known natural radioactive source but fall into the ranges expected for superheavy nuclides: were the superheavies already there. fission tracks discovered in lead glasses were tentatively attributed to element 114. Even lower limits down to can be reached by etching .8. This study predicted continuation of the process up to sufficient to feed Z=114. Although now extinct. but unrecognized? 2. and low-level counting techniques did not reveal any activity above background.35]. contain superheavy nuclei with half-lives down to some In this context. Relevant geochemical aspects were discussed in Refs. a search for element 110. In Dubna. eka-platinum. eka­ lead. The question remained controversial for quite some time [32]. there was hope to discover them in Nature. assuming a half-life of y for the radioactive source. Historical Reminiscences 297 numbers.1 TERRESTRIAL SAMPLES Any search for superheavy elements in terrestrial material begins with the choice of a sample. however. present at a concentration of to gram per gram of sample. but further measurements [37] of thin samples sandwiched between two plastic fission-track detectors showed that the events were background caused by cosmic-ray induced reactions of lead. Examinations of the same and of other lead-bearing samples for spontaneous fission events with large proportional counters in Dubna seemed to confirm these findings. This latter convention is also followed here for comparison of results of such “search for” experiments. years. Other early treatments [29­ 31] denied the production of superheavy elements in the r-process. Figure 4 resulted [28] for a stellar temperature of a and a cycle time of only 8 s for the whole neutron density of process. they may have left detectable traces such as fission tracks or fission products in certain samples. In Berkeley.

Thus. an unlikely situation. it can detection is less efficient than fission fragment or compete because much larger samples. can be inspected. Furthermore. but with identical rates. Such neutron bursts can be recognized by recording neutron multiplicities – events with several neutrons in coincidence – with counting tubes [43. Activities were indeed found with metallic platinum to bismuth. Although neutron counting. the neutrons were due to cosmic-ray induced nuclear reactions during the counting operation. the rates fell on a curve representing relative cross-sections for high-energy spallation reactions as a function of atomic number. allowing a sensitivity of quick survey of a great variety of samples.298 The Chemistry of Superheavy Elements internal fission tracks in suitable minerals. where they were accumulated over millions of years. Searches [35. More advanced applications of neutron counting were based on the expectation that spontaneous fission events of superheavy nuclei should be accompanied by the emission of about ten neutrons [41. distinctly more than two to four observed for any other spontaneous fission decay. .44] or large tanks filled with a liquid scintillator sensitive to neutrons [45].39] remained inconclusive in a variety of minerals containing heavy elements including lead.42]. With a simple arrangement of six neutron counters. a was reached [40] in two days of counting. A more generally applicable technique for spontaneous fission detection is counting of the neutrons emitted in the fission process. up to tens of kilograms. as Figure 5 shows. however.

The solvent does not evaporate. The tubes were embedded in paraffin for slowing down the neutrons. a negative pressure develops in the solution through the action of centrifugal forces. The publication gives an illustrative example how researchers were misled for some time by a tiny contamination of a sample by the synthetic 2. Historical Reminiscences 299 Figure 6 shows a multiplicity detector [43] with twenty counting tubes arranged in two rings around the central sample chamber which accommodated up to 100 kg of a sample. The instrument. however. Upon rotation. such detectors were operated below ground and with an electronic anticoincidence shielding triggered by incoming high-energy particles. A quite unconventional approach to internal fission-event detection was a device called the spinner. A similar sensitivity was reached [45] with a scintillator-based neutron detector. Figure 7. To suppress background by cosmic-ray induced neutron showers.5-y common as a source of spontaneous fission events in research laboratories. consists of a glass cylinder with glass arms filled with about one liter of the sample solution. Bursts neutrons in the sample at an emitter concentration of should result in about one event per day with multiplicity four or larger. With the latter instrument [45] no positive results at the level were obtained for lead ores and samples from industrial lead processing. but remains in a metastable .8. It operates on the same principle as the cloud chamber.

the final samples were exposed to neutrons but no fission events were found with track detectors. The spinner can be operated at rates as low as one event per month corresponding to the detection of to of a spontaneous fission activity.300 The Chemistry of Superheavy Elements state until a strongly ionizing event in the solution destroys this state and produces a bubble which is detected optically. After the unsuccessful inspection of hundreds of samples with highly sensitive techniques attempts were made to improve the sensitivity of such searches by enrichment of superheavy elements from very large quantities. The deduced concentration limit of to is the lowest ever achieved in searches in Nature. hence. and fractions eluted from the resin showed rates up to five events per day with neutron multiplicities as depicted . After processing of some spring water through 850 kg of an anion exchange resin. The extreme case [47] was a search for element 114 in flue dust collected during the industrial processing of to tons of galena. a weak spontaneous fission activity appeared in the resin. They thus may carry superheavy elements of deposited in deeper layers of the Globe. After further concentration by chemical and mass separations. Among the “hottest” natural samples were brines from hot springs at the Cheleken Peninsula in the Caspian Sea which are known to be rich in volatile elements. be enriched in flue dust. probably due to the collection of material escaping from large depth in the Earth’s mantle. Eka-lead should be more volatile than lead and. No such events were observed [46] in salts of platinum to lead and natural lead sulfide (galena).

giant halos were observed [52] with ranges an energy predicted for nuclides equivalent to about 14 MeV around element 126. and are due to radiation damage by escaping from radionuclides enclosed in the grain. Figure 9. A search for such activities in similar brines. Radioactive halos are a known phenomenon since the early days of radioactivity research. Cuts through such halos reveal a ring structure with diameters corresponding to the ranges in the host mineral of particles from the natural decay series. In particular. Historical Reminiscences 301 in Figure 8 [48]. natural can be ruled out as the source.8. Salton Sea in California and Atlantis II at the floor of the Red Sea. in biotite from Madagascar. ranges which cannot be associated with known natural radionuclides. but not a contamination by 2. gave no positive evidence [50]. Evidently. They are found in certain minerals as spherical zones of discoloration around a central mineral grain. Very unexpected news arrived in the summer of 1976: Evidence for element 126 and possibly 124 and 116 in Nature was reported [51] in a study of giant radioactive halos in biotite. however. Such halos have as central grains relatively large crystals of monazite. . There are. a lanthanide-thorium-uranium phosphate.6-y Attempts to concentrate the activity for identification of its atomic number failed [49].

As can be seen in Figure 10. The concentrations of the superheavy elements. much weaker peaks are identified and assigned to the x-rays of elements 126. 116 and 124. the occurrence of elements 126 and 124 in monazites would not be unlikely because they should be homologues of uranium and thorium [14].302 The Chemistry of Superheavy Elements In order to verify the supposed presence of elements around monazite inclusions were irradiated with a sharply collimated proton beam and the proton induced x-ray spectra of the elements were recorded. Since polonium is known to be strongly enriched by some marine invertebrates. In the concept of a superactinide series of elements.g. were surprisingly high. it was suggested [54] to search for element 116 in crustacea . the L x-rays of uranium and thorium. at Indian beaches. e. from about 24 to 29 keV energy. as estimated from peak intensities. If such concentrations would also hold for bulk monazite. In between. tons of superheavy elements would be easily accessible in some regions. Element 116 is expected to be a homologue of polonium. and the K x-rays of the lanthanide elements. two well separated groups of strong peaks appear [51]. 10 to 100 ppm.

the evidence for superheavy elements vanished [57. attempts failed [59] to detect them in bulk monazites through isolation of an A>294 fraction with a mass . When a more specific technique for the excitation of x-ray spectra was applied to the inclusions.8. namely by monochromatic synchrotron radiation tuned to the x-ray absorption edges. Objections against these findings were soon raised. and crabs in coastal waters at beaches rich in monazite sand – perhaps a gourmet’s recommendation. Furthermore.58]. The weaker peaks were shown to stem from to K x-rays from traces of ordinary elements such as antimony and tellurium [56]. The strongest peak attributed to element 126 could experimentally be accounted for [55] by a prompt from the (p. Historical Reminiscences 303 such as lobsters. shrimp.n) nuclear reaction with natural a major component of the monazite crystals.

68] in such meteorites and enriched [66] in the tiny host phase although they are not formed in fission. The strange xenon was found to be strongly enriched [66] in a host phase comprising less than 0. Much attention was paid to evidence for extinct superheavy elements in a class of primitive meteorites. Such “search for” experiments coincided with studies of the heavy element abundances in the cosmic radiation. These are lowtemperature condensates from a solar gas that have more or less escaped reheating and other differentiating processes and may. remained controversial for years [69]. A survey [33] of all data obtained until 1970 showed one single . The conclusion is that giant halos are not due to superheavy elements. carried out by exposure of particle track detectors – nuclear emulsions or plastic sheets – in balloon flights to high altitudes and analysis of the recorded tracks for atomic number and abundance. In the Allende meteorite available in large quantities. samples of primitive meteorites were inspected by neutron multiplicity counting. Stimulated by these studies. bismuth and indium in meteorites. Whether there are at least two anomalous xenon components of different origin. a weak fission activity at the level was reported [71-73] but could not be chemically enriched [74-76]. which are abundant fission products. represent the stuff from which the solar system was made. Eventually. the carbonaceous chondrites.304 The Chemistry of Superheavy Elements separator. isolated after dissolution of the bulk in strong acids.5 % of the meteorite. but a generally accepted explanation what they are is still lacking.63] that superheavy elements might be the progenitors. This hypothesis was supported by correlations [64] between the concentrations of excess xenon and of volatile elements such as thallium. However. thus. Chemical treatments [60] of large bulk samples also remained without success. a suspicion later narrowed to elements 115 or 114. 2.2 EXTRA-TERRESTRIAL SAMPLES No indications of spontaneous fission activities on the moon surface were obtained by neutron multiplicity counting of 3 kg of lunar rocks [45].67. 113 [65]. light xenon isotopes from 129 to 124 were also over-abundant [61. it was suggested [62. the fission origin of the anomalous xenon was ruled out [70] because in a host phase containing the excess xenon no enrichment was detected for the adjacent barium isotopes 130 to 138. which pointed to the homologues elements 111 to 116. They contain a surplus of the neutron-rich xenon isotopes 131 to 136 [61] first attributed to spontaneous But when this assignment became questionable fission of now extinct after closer inspection.

Examples for fusion-evaporation reactions are and at that time tried in Berkeley and Dubna.45] for spontaneous fission activities by counting nodules with neutron detectors. but no evidence was obtained [40. New types of reactions – . the yields of fusion products are much lower than expected according to the cross sections for compound nucleus formation. As a precaution. respectively. A similar limit was deduced [78] after exposure in a satellite. In order to initiate fusion. larger projectiles with at least twice as many protons and neutrons are required. This problem stimulated systematic studies of heavy-ion reactions all the way down from the first touch of two interacting nuclei until final fusion. Fission tracks were found [83] in feldspar inclusions in such nodules. the limit became more stringent: no superheavy nucleus in spite of recorded 204 tracks with atomic number 74 to 87 [77]. Early Attempts to Synthesize Superheavy Elements First attempts – in the early seventieths – to produce superheavy nuclei by nuclear synthesis in the laboratory were based on complete fusion of a projectile and a target nucleus chosen to attain by amalgamation the proton number of the desired element. In a study of cosmic-ray induced tracks in olivine crystals enclosed in iron-stone meteorites and. so that the compound nucleus retains excitation energy. which is high enough for the prompt evaporation of several neutrons. The largest collector surface for elements impinging on the Globe is the sea.8. hence. This energy is not completely consumed in the nuclear reaction. for the discovery of element 104. In such heavy systems. 3. the excitation energy of the compound nucleus is kept as low as possible by choosing low projectile energies. Historical Reminiscences 305 event beyond With the data collected in the Skylab space station. It soon became obvious that in such reactions the deficit in the yields is even larger than can be explained by post-fusion losses. exposed in space over millions of years. of course. unusually long tracks were found and attributed [79. close contact between projectile and target is required. but this conclusion could not be maintained [81. iron-manganese hydroxides. The projectile has to carry sufficient kinetic energy to overcome the mutual electrostatic repulsion between the two partners. The deficit is attributed to past-fusion losses by fission of the compound nucleus and at the intermediate steps in the evaporation chain. For the synthesis of superheavy nuclei by complete fusion. Heavy elements deposited in seawater are enriched in certain sediments such as manganese nodules.80] to superheavy elements.82] after calibration experiments with energetic beams at accelerators.

This hindrance of fusion becomes significant especially for systems with a large total number of protons. 3. any positive evidence for superheavies could only be considered as a first hint and would call for further examinations. when very heavy projectiles such as uranium became available at the Darmstadt UNILAC in the middle of the seventieths. e. The partners first stick together in a dumbbell-shaped. with nuclides of known elements – very successful for the identification of new actinide elements – were not possible. as in superheavy element syntheses [25]. and with fission fragment detection half-lives not attributable to known spontaneous fission activities were looked at. Hence. In the early experiments identification of synthetic superheavy nuclei was spectroscopy. and this deficit would further increase by . mainly attempted by radioactivity detection. through radioactive decay. A principal problem was that – in the view at that time – the searched-for island would be completely isolated from known heavy nuclei by a region of instability against prompt fission. Because of the complexity of the reaction product mixtures.306 The Chemistry of Superheavy Elements called deep-inelastic reaction and quasi-fission – turned out to play a significant role. Thus. so that with some probability one side can grow on the expense of the other one. additional selective steps were often included. The results are broad distributions of proton and neutron numbers and also excitation energies in the reaction products. but the electrostatic repulsion between the partners drives the complex apart before amalgamation to a compound nucleus can occur. On the other hand.1 COMPLETE FUSION REACTIONS As long as elements around 126 were the goal. Its neutronto-proton ratio cannot be achieved by any realistic projectile-target combination.85]. such as chemical or mass separations. cross sections as large as tens of millibarn reaction. dinuclear collision complex. the perspectives for superheavy element synthesis by complete fusion reactions looked very promising. assignments of new elements by their connection. which rotates. In this intermediate state nucleons are exchanged between the partners. were extrapolated [84. leading to premature claims which soon disappeared again. Based on data for the production of heavy actinides and without knowing the fusion hindrance. a requirement not always followed during this gold-rush period. for the However. Close approach to Z=114 means that the neutron number remains far below N=184. With signals in the energy range expected for superheavy nuclei were searched for. with element 114 in the focus the situation became different in that the doubly magic Z=114. N=184 is extremely neutron rich.g. such incomplete transfer reactions offered an alternative approach to reach superheavy elements.

very surprising news appeared: can superheavy nuclei be made by heavy-ion reactions without using a heavy-ion accelerator? From tungsten plates bombarded over long periods in the beam dump of the 24 GeV proton beam at CERN Geneva. the magnetic rigidity. neutron-rich target – with projectiles. a weak. glass or polymer sheets to produce tracks of spontaneous fission events. With the larger variety of heavy-ion beams soon becoming available. The whole product mixture was collected on a catcher foil and exposed to mica. eka-mercury [92]. On the other hand. This was taken as an indication [89] for the synthesis of a compound nucleus of element 126. In these ambitious experiments. high-Z. Whereas most of the early fusion studies employed relatively light projectiles and heavy targets. High-energy 13 to 15 MeV energy – as predicted for elements around 126 – from short-lived emitters were observed at the ALICE Orsay in bombardments of thorium with krypton. more symmetric combinations were also investigated. and it should evaporate four neutrons to probably located outside the island. Within a few years. The experiment was negative at a cross section limit of contains only 174 about 10 nanobarn. kinetic energy and time-offlight of fragments from and interactions were measured. Production by a two-stage process was postulated: . Fusion of with and aimed at the synthesis of the elements 122 and 124 was studied at Dubna [88] without positive results. A few examples may illustrate this exploratory period. long-lived spontaneous fission activity was chemically isolated in the mercury fraction and assigned to element 112. The detection techniques applied in those early attempts were often surprisingly simple searches for spontaneous fission activities. such as which could fuse to element 127 [91]. In this time. attempts to reach the island by complete fusion reactions were carried out on a broad basis. But attempts in the same laboratory to secure the evidence by a direct mass identification failed [90]. Historical Reminiscences 307 evaporation of several neutrons from the compound nucleus to products located close to the border or even outside the anticipated stability island. this technique allows the detection of short-lived nuclides down to millisecond half-lives [88]. The first attempt to synthesize element 114 was made in 1969 in Berkeley [10] by bombarding – a synthetic. to meet N=184 would require an overshooting of Z=114 by about ten protons [84.86]. By quickly rotating the catcher between detector foils during bombardment. The compound nucleus neutrons. twenty different reactions were tried [24] covering compound nuclei with proton numbers from 110 to 128 and neutron numbers from 168 to 194.8.

The region of very short-lived nuclei (curves 1 and 2) was inspected with two recoil-fragment separators with fragment detection in surface-barrier detectors.97] targets of were bombarded.19 % natural abundance) and expensive. It should start at by with a few seconds half-life. The cross section limit achieved was about 200 picobarn with some extra sensitivity gained for long-lived products by fission fragment-fission neutron coincidence counting [101]. For intermediate half-lives (3 to 5). The reaction was generally considered to be most promising for the synthesis of superheavy elements because the compound nucleus Z=l 16. but again without any magnitude – from 1 evidence for superheavy nuclei.93.308 The Chemistry of Superheavy Elements generation of a broad distribution of energetic recoil atoms by protoninduced spallation of tungsten. In the Figure. After this first round of fusion experiments. a conclusion finally shared by most of the original authors [95]. and off-line chemistry for long-lived products (6 to 8). With a variety of techniques. the decay chain after evaporation of four neutrons was expected [12] to be suitable for detection. rare (0. . N=180 provides at a moderate overshooting of the proton shell a relatively close approach to the neutron shell. and too low decay rates at longer half-lives. In Figure 11 we refer to a later elaborate series of experiments performed by a large international collaboration [100] at the UNILAC and the SuperHILAC. Each technique has a region of highest sensitivity. the resulting upper limits of the production cross sections are plotted as a function of the assumed halflife. N=28). limited by decay losses before isolation at shorter. At Berkeley [96. chemical on-line separations were applied. Also. followed by fusion of such atoms with tungsten. Attempts to confirm the results in other laboratories were unsuccessful [46. a half-life range of 14 orders of to 10 y – was covered. Anion exchange of bromide complexes (5 and 7) was applied for 108 to 116 [18]. The reaction with a Z=119 compound nucleus was also studied [102] with negative results. followed within several and minutes by two electron captures in and ends at by spontaneous fission with a 50 min half-life. and at room temperature (4 and 6) for 112 and 114 [19]. further efforts were focused on experiments with as projectile.99].94]. The chemical procedures were based on volatilization at high temperature (3 and 8) aimed at elements 112 through 116 [17]. a very neutron-rich and doubly magic isotope (Z=20. at Dubna [98.

now with positive evidence for the formation of (see Ch. But the production cross section is two orders of magnitude below the level reached in the previous studies. Historical Reminiscences 309 The system has recently been reinvestigated at Dubna [103]. the question was: Is production the problem or is it survival – nuclear reaction or nuclear stability? Are the cross sections too low or the half-lives too short? These recent results would point to the production as the key problem. they would give a hint why so many attempts to make superheavy elements by complete fusion failed.. e. Over the years. 1).2 INCOMPLETE TRANSFER REACTIONS Would incomplete transfer processes open an alternative approach to the synthesis of superheavy nuclei? Would. 3.8. The halflives in the postulated decay chain – milliseconds to seconds – fall into the region covered in Figure 11.g. in the collision of two nuclei one partner take up enough protons and neutrons to grow to the doubly magic whereas the complementary partner would shrink to a known neutron-rich isotope of ytterbium? . If these results can further be substantiated.

. associated with broad distributions of neutron numbers and excitation energies. beyond uranium. an extrapolation for surviving Z=114 fragments gave about 10 picobarn cross section [25].310 The Chemistry of Superheavy Elements A radiochemical study [104] of the element distribution in the reaction at the UNILAC revealed the expected broad distribution of reaction products. The Z<92 distributions should be reflected in complementary Z>92 distributions. However. As is shown in Figure 12. a not completely hopeless situation. where losses by sequential fission of transfer products are not significant. the production cross sections of surviving transuranium nuclides decreased from plutonium to fermium by eight orders of magnitude. Below uranium. By extrapolation of the model to Z=70 nuclei about 100 microbarn total production cross section resulted. This trend was well reproduced [105] by a theoretical model treating nucleon transfer in the intermediate collision complex as a diffusion process. the observed yields decreased exponentially from Z=92 down to Z=73. Nonetheless. including the Z=114 isotopes. fission of the freshly formed transfer products becomes very significant and leads to severe losses.

The curve labeled CHEM [106] was obtained with off-line chemical separations [107] spontaneous fission activities. The curve labeled GAS holds for an on-line search [108] for components volatile at room temperature. All these efforts remained without positive evidence. too [111].8. WHEEL [106] refers to fission track detection in the unseparated product mixture deposited on a rotating catcher. Attempts to detect short-lived nuclides were less sensitive. The data are summarized in Figure 13. Attempts to find superheavy elements in the reaction failed. although the production cross sections for transcurium isotopes increased by three orders of magnitude [112] compared with the reaction. here. Historical Reminiscences 311 Direct searches for superheavy elements in the reaction were undertaken at the UNILAC by several groups. the 10 picobarn and an assay for level was reached for half-lives between several days and years. and JET to on-line transport from target to detector with a gas jet [91.110]. . REC [109] to implantation of recoil atoms in a surface barrier detector.

Hence. the extrapolated halflives of nuclides closer to the magic nuclei went down. initiated in 1981 at the UNILAC by the synthesis of element 107 [113]. Although in all cases the claims could not be substantiated. further searches for superheavy elements in Nature appear to be rather hopeless. to about ten days for Z=l 10. After so many unsuccessful attempts to discover the island of superheavy nuclei. Instead of using chemical methods as a tool to discover unknown elements.312 4. from systematic scanning of large numbers of samples to quite unconventional experiments. they forced the researchers to push physical and chemical detection techniques to levels not achieved before. From then on expansion of the Periodic Table happened in a systematic element-after-element approach.g. With an increasing data base for very heavy nuclei. 1). In the early eighties. But for the participants it was an exciting time. e. Claims for success were raised from time to time and challenged for better experiments to prove them. the exploratory period came to an end. emitters extends from the Nowadays. they now apply their know-how to explore the unknown chemistry of already known elements at the end of the Periodic Table. the exploratory period of superheavy element research may appear as a sequence of frustrating failures. N=184 [114]. with a broad range of approaches. The chemists involved in searches for short-lived superheavy elements have since changed their emphasis. . the landscape sketched in Figure 3 has changed completely (see Ch. a ridge of short-lived peninsula of known nuclei to the region previously considered as an island. The Chemistry of Superheavy Elements Epilogue In a condensed retrospective as presented here. extensive experimental and theoretical studies of the relevant nuclear processes were undertaken to provide a better knowledge. Since then.

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311 Recoil atoms Recoil fragment separators 308 299 Spinner detector X-ray spectroscopy 302. 305. 307 Element 126 306 Element assignment Element-after-element 312 307 Exploratory studies Fusion hindrance 305. 292 292 Spontaneous fission 292 292 Occurrence in Nature 293 Decay chains Extinct superheavy elements 297 Half-life requirements 292. 297 Spontaneous fission detection 293 296 Supernova explosions Review articles 295 292. 311 300. 293 291 292. 303 Mass separation 304.8. 303. 304. 300. 297. Historical Reminiscences Index 317 Chemical properties Electron shell configurations 295 Periodic Table. 296. 293 292 291 291 Synthesis by fusion reaction 307 reaction 308. 309 raction 308 reactions 308 reactions 307 307 At a proton accelerator 306 Element 114 306. 309 Fusion-evaporation 305 294 General aspects 294 Heavy-ion accelerators Neutron number 184 306 . positions in 295 295 Prediction of properties 295 Relativistic effects 295 Superactinide elements Detection techniques Chemical separations 300. 311 Fission neutrons 298. 308 Fission tracks 293. 308. 297 293. 312 Perspectives nucleosynthesis 296. 298. 305 Particle tracks 308. 305. 307. 300. 303 Extra-terrestrial samples Excess xenon in meteorites 304 Extinct superheavy elements 304 304 Heavy cosmic radiation 305 Iron-stone meteorites 304 Lunar rocks 305 Marine sediments 304 Primitive meteorites Nuclear properties Decay half-lives Early speculations Element 110 Element 114 Element 126 Fission barriers Island of superheavy nuclei 292 Neutron shell closures 291 Proton shell closures 291.

299. 302. 304 Large scale operations 300 Monazites 301. 311 reaction 311 Collision complex 306 Exploratory studies 311 Mechanism 306. 303 First searches 297 Flue dust from lead mining 300 Giant radioactive halos 301. eka-platinum 297. 298.318 The Chemistry of the Transactinide Elements Element 114. 309 Superheavy nuclides 311 Transcurium nuclides 310 Terrestrial samples Brines from hot springs 300 Element 110. 303 Synthesis by transfer reaction 310. eka-lead 297. 302. 124. 302. 116 301. 300 Elements 126. 300 .

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