Inhaltsverzeichnis

Vorwort

Preface

Throughout my life's work in science I have been greatly influenced by the standing problem of synthesis and studies of the heaviest chemical elements. In 1960 I joined the then-young Laboratory of Nuclear Reactions of the Joint Institute for Nuclear Research at Dubna. It was headed by G. N. Flerov who, with K. A. Petrzhak, discovered the spontaneous fission of uranium. The laboratory was equipped with a powerful cyclotron which could accelerate boron and heavier ions to energy of some 10 MeV per nucleon. A most ambitious goal was to discover new chemical elements. The first "planned" new nuclide, ²⁶⁰104, was expected to be produced by the bombardment of ²⁴²Pu with ²²Ne. Estimates of its half-life were very uncertain, spanning many orders of magnitude. Necessarily, the initial emphasis was on physical methods of identification of the atomic and mass numbers because, in general, the physical techniques are effective down to very short lifetimes. On the other hand, element 104 was also of great interest for chemists. It was expected to be the first "transactinoid," resembling in its properties hafnium, the first "translanthanoid." As such it would strongly differ in chemical properties from all the lighter transuranium elements. This might facilitate and accelerate its chemical identification, which is an independent reliable method for the assignment of the atomic number and could eventually strengthen the primary physical evidence. The chemical identification of element 104 was the first task I got involved in. It was soon recognized that, with the availability of only one short-lived atom at a time, the processing of the accelerator bombardment products must be continuous and allow immediate chemical transformation of the new atom, once created. The goal was to achieve this, as well as the subsequent chemical isolation of the new molecules, in less than a second, which was the optimistic higher limit of t1/2 . Also required was highly efficient detection of the decay events of element 104 because the expected production rate was, by orders of magnitude, smaller than for any previous element. The more unusual was the combination of all these musts. The existing exclusively batchwise isolation techniques for hafnium and most other metallic elements took at least minutes to accomplish.

Our team did not see prospects of achieving the goal by simply upgrading the existing methods. In those times An. N. Nesmeyanov, head of the Chair of Radiochemistry at the Moscow University, consulted the Flerov's laboratory in Dubna on radiochemical problems. He pointed to the expected considerable volatility of higher halides of the transactinoid, compared with that of similar compounds of actinoids, as a possible basis of fast separations. When seeking an experimental method which would make the most of the dissimilar volatility, I benefited from the experience and ideas I gained as a student of Professor Nesmeyanov. In his laboratory I separated various volatile brominated methanes to solve a problem in "hot atom chemistry." After a few years our small group of chemists did come with an efficient technique capable of isolating hafnium as tetrachloride in tenths of a second. The method combined the principles of hot atom chemistry and gas-solid chromatography. We successfully applied it to element 104 and subsequent transactinoids. A generation later, around 1990, other world laboratories involved in transactinoid studies also started experiments with gaseous compounds. Fortunately, all the transactinoid elements up to Z = 118 must either be volatile in elemental state or form some characteristic volatile compound(s), so that the gas phase techniques are a universal research tool in radiochemistry of the transactinoid elements.

The aim of this book is to outline and analyze some fundamental aspects of the work performed at Dubna and elsewhere, and to discuss prospects for the future.

My sincere thanks go to my colleagues: V. Z. Belov, Yu. T. Chuburkov, V. P. Domanov, B. Eichler, S. Hübener, M. R. Shalaevskii, L. K. Tarasov, A. B. Yakushev, B. L. Zhuikov, T. S. Zvarova - my wife, and others. Together we pioneered and conducted transactinoid studies as well as tried to analyze the fundamental aspects of what we were doing - the gas phase radiochemistry of metallic elements. We were a small group of chemists embedded in a large physical laboratory. Hence, it was of decisive importance for us that the late Prof. G. N. Flerov put much emphasis on the role of chemical identification of new elements. He actually initiated, and then invariably supported, radiochemical studies in the Dubna laboratory.

Klappentext

The Inorganic Radiochemistry of Heavy Elements

The aim of this book is to facilitate the wider use of advantageous gas phase techniques towards heavy elements. Studies of the transactinoid elements (polyvalent metals) stimulated application of their volatile halides, oxides, and oxyhalides to fast radiochemical separations. Selected results are presented here. Primarily, this book features the physico-chemical basis of experimental methods and techniques. It focuses on evaluation of the desorption energy from data of a single gas-solid chromatography experiment through calculation of desorption entropy. Heterogeneity of the column surface and its chemical modification are taken into account. Several approaches to the estimation of bulk properties of the compounds from experiments with only a few atoms are also discussed. The accuracy of the derived quantities is then analyzed using the Bayesian statistical approach.

The book is aimed at newcomers to the field as well as experts actively engaged in this area of research.

ISBN 978-1-4020-6601-6

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Author Index

A

Acosta, J.J.C., 23
Altynov, V.A., 20
Ans, R., 95

B

Bächmann, K., 10, 19, 28, 30, 126, 128, 138, 178
Bakaev, V.A., 148, 166
Baltensperger, U., 11
Barberi, R., 144
Barth, J.V., 159
Bartolino, R., 144
Belov, V.Z., 8, 26, 64, 126, 193
Berg, E.W., 23
Bernasconi, M., 150, 154
Blachot, L.C., 28
Bombi, G.G., 94
Bonvent, J.J., 142, 144
Borg, R.J., 194, 195
Boussières, G., 3
Brüchle, W., 15, 16, 199, 200, 205
Bukin, A., 197
Buklanov, G.V., 8, 64

C

Caletka, R., 6, 63, 78, 203
Capelli, L., 144
Chelnokov, L.P., 8, 64
Chepigin, V.I., 29
Chuburkov, Yu.T., 4, 6, 63, 78, 203
Chun, K.S., 29
Currie.L.A., 199
Czerwinski, K.R., 13

D

De Angelis, A., 199
DeBoer, J.H., 127, 130, 141
Debye, P., 42, 161
Dienes, G.J., 194, 195
Di Marco, D.B., 94
Domanov, V.P., 8, 18, 29, 64, 126, 193
Dressler, R., 15, 16, 199, 205
Düllmann, Ch.E., 14-16, 40, 59

E

Eberhardt, K., 15, 16
Eichler, B., 15, 16, 26, 28, 29, 113, 138, 181, 205
Eichler, R., 15, 16, 117, 205
Evans, M.G., 67

F

Fedoseev, E.V., 23
Fehnse, H.F., 10
Fishlock, T.W., 158
Folden, CM., 59
Frischat, G.H., 146, 147

G

Gäggeler, H.W., 11, 13, 15-16, 28-29, 113, 124, 205
Gäggeler-Koch, H., 29
Gartner, M., 205
George, S.M., 151
Giddings, J.C., 41, 93
Gilliland, E.R., 40, 41
Ginter, T.N., 15, 16
Glaus, F., 15, 16
Gnielinski, W., 50
Gorlov, Yu.I., 156
Gormley, P.G., 47
Goss, A., 146, 147
Gregorich, K.E., 13, 15, 16, 205
Greulich, N., 28, 29
Guillamont, R., 194
Gupta, P.K., 142, 144

H

Hamann, D.R., 151
Hambleton, F.H., 151, 152
Haukka, S., 157
Heide, G., 146, 147
Helene, O., 199, 200
Henderson, R.A., 13
Henke, L., 145
Herrmann, G., 29
Hickmann, U., 10, 28, 29
Hill, T.I., 169
Hockey, J.A., 151, 152
Hoffman, D.C., 15, 16
Hohn, A., 117
Hübener, S., 19, 23, 24, 205
Hussonnois, M., 8, 26, 64

I

Illas, F., 152
Inglesia, E., 147, 148, 169, 176
Inniss, D., 144
Iori, M., 199
Isted, G.E., 158

J

Jäger, E., 15, 16
James, F., 199
Jin, K.U., 137
Jonsson, J.A., 93
Jorgensen, J.W., 95
Jost, D.T., 11, 13, 15, 16, 205

K

Kadkhodayan, B., 12
Kennedy, M., 47
Kim, U.J., 20, 21
Kirbach, U.W., 15, 16
Kiselev, A.V., 148
Knaupp, S., 142
Knudsen, M., 87, 112, 114, 115
Kolatchkowski, 97
Korotkin, Yu.S., 8, 20, 26, 64
Kosanke, K.L., 79
Kovacs, A., 11
Kovacs, J., 13
Krivanek, M., 4
Krull, U.J., 145
Kurkijan, CR., 144

L

Lan, K., 95
Le Naour, C, 195
Lebedev, V.Y., 205
Lebedev, V. Ya., 185, 205
Lee, D.M., 15, 16
Lee, W.T., 158
Leonardelli, S., 149
Lindemann, FA., 42
Lopez, N., 151, 152
Lygin, V.l., 153

M

MacLellan, J.A., 199
Masini, P., 150, 154
McDaniel, M.P., 157
Merinis, J., 3

N

Nagy, N., 145
Nitsche.H., 15, 16
Novgorodov, A.F., 97

O

Orelowich, O.L., 20

P

Pacchioni, G., 152
Pantano, CG., 150
Patin, J.B., 15, 16
Patrikiejew, A., 162
Pershina, V., 15, 16, 178, 205
Piguet, D., 15, 16
Poggemann, J.F., 146, 147, 150
Polanyi, M., 67
Pollard, W.G., 114
Porstendorfer, J., 81
Porter, F., 197
Prosper, H.B., 199

Q

Qin, Z., 15, 16

R

Radlein, E., 146, 147
Rarivomanantsoa, M., 151
Reichsmann, 192
Rengan, K., 28
Righetti, P.G., 144
Roos, M., 199
Rudolph, J., 28, 30

S

Samhoun, K., 22
Schädel, M., 15, 16, 113, 205
Schausten, B., 15, 16
Schegolev, V.A., 8, 64
Schimpf, E., 15, 16
Schmidt, K.H., 202
Schmidt-Ott, W.D., 10, 72
Schott, H.-J., 15, 16
Schrewe, U.J., 10
Schrijnemakers, P., 156
Semenov, N.N., 67
Seward, N.K., 15
Shalaevski, M.R., 126, 193
Shalaevskii, M.R., 6, 26, 78, 203
Shalayevsky, M.R., 8, 64
Shannon's, R.D., 140
Shchegolev, V.A., 26
Sherer, U.W., 13
Shilov, B.V., 5
Sneh, O., 151
Souza, S.D., 150
Soverna, S., 15, 16
Stallons, J.M., 147, 148, 169, 176
Steele, W.A., 48
Steffen, A., 19, 128
Stender, E., 79
Strellis, D.A., 15
Strom, D.J., 199
Sudowe, R" 15, 16
Suglobov, D.N., 23

T

Taut, S., 205
Taylor, G.I., 95
Thorle, P., 15, 16
Timokhin, S.N., 9, 15, 16, 20, 21, 29, 185,
Trautmann, N., 15, 16, 29, 205, 206
Travnikov, S.S., 23
Trubert, D., 195
Tunitskii, N.N., 97
Türler, A., 11, 13, 15, 16, 205

V

Vahle, A., 15, 16, 72, 182, 205
Van Der Voort, E., 156
Vansant, F., 156

Vedeneev, M.B., 185
Vermeelen, D., 11, 13
Vitiello, M, 152
Von Dincklage, R.D., 10

W

Wadsak, M., 158
Weber, A., 11, 13
Wirth.G., 15, 16

Y

Yakushev, A.B., 9, 15, 16, 185, 205

Z

Zhuikov, B.L., 29, 74, 99, 100
Zhuravlev, L.T., 148, 149, 151
Zielinski, P.M., 15, 16
Zvara, I., 4-6, 8, 9, 21, 24, 26, 27, 29, 63, 64, 68, 77, 78, 89, 101, 102, 104, 106-108, 126, 127, 137, 185, 193, 203, 205, 208, 211
Zvarova, T.S., 4, 26, 27, 63, 78
- Subject Index

A

Actinoids (definition), xxiii

Adsorption. See Adsorption enthalpy; Adsorption entropy; Adsorption thermodynamics; Chemisorption; Physical adsorption
- localized, 114, 122-124, 126, 132, 133, 135, 141, 162, 164-166, 174, 180
- intermediate, 133, 162, 164, 173
- mobile, 112, 116, 122-124, 127, 130, 133, 135, 136, 138, 141, 162, 164, 165, 173, 174
Adsorption enthalpy (experimental) by Second Law
- from retention times in IC, 124
- from retention times in temperature programmed chromatography, 125
- from survival yield of short-lived nuclides in IC, 124
- from thermochromatograms at different run duration, 125, 126
- sample measurements, 126-128
Adsorption enthalpy (experimental) by Third La ideal surface, mobile adsorption - calculation formulae for IC, 135
- calculation formulae for TC, 135-137
- correlation of the values with sublimation enthalpies, 71, 138, 139, 178
- proximity of the values to sublimation enthalpies, 138, 139, 178
- - rationale lacking, 128, 140, 172, 174, 177
- real surfaces require revision of the values.
- See Desorption energy data by Third Law Adsorption enthalpy from experimental data, on heterogeneous surface.

- See Desorption energy from experimental data
Adsorption entropy. See also Partition functions

- entropy of adsorbate on homogeneous surface from statistical mechanics, 131-134
- - mobile model, 131, 132
- - localized model, 132-134
- - accounting for surface diffusion, 163-165
- on heterogeneous surface, 169-171
- on homogeneous surface localized adsorption, 134
- - localized adsorption with surface diffusion, 163-165
- - mobile adsorption, 131, 132
- - uncertainty due to postulating unchanged internal entropy, 162, 163
- quality of experimental values, 127, 128
Adsorption isobar, 89, 100, 126, 127, 209
Adsorption sites, 122, 132, 159, 164-166, 179, 181
- active, 60, 192
- blocking by reagents, 60
- number concentration of, 122, 133
- - possibly overestimated, 174
Adsorption sojourn time. See Physical adsorption;

Adsorption thermodynamics

- adsorption reference states, 162
- adsorption standard states, xxii, 127, 131, 133, 134, 181

- - fractional surface coverage, 123

- - molar area, 122, 123, 131, 133

- - molar volume, 122, 123, 127, 131

- distribution coefficient (dimensional), 121

- - from experiments in uniform isothermal column, 121
- equilibrium constants (dimensionless), 121

- - for ideal mobile adsorption model, 122, 123

- - for ideal localized adsorption model, 122, 123

- - for real surfaces, effective, 167, 169, 171, 175, 177, 178
Aerosols
- coagulation rate, Smoluchowski equation, 81
- diffusion coefficient, 44, 45
- Cunningham slip factor, 45
- diffusional deposition of. See Diffusional deposition in channels generators (production), 10, 11, 79, 80
- gravitational settling, 80, 84
- materials of, 10-12, 72
Aerosol flow transportation, 9-12, 79-82
- deposition of particulates by impact, 12, 79
- optimal size of particulates, 80, 81
- - necessary lower limit of concentration, 81
- reclustering at IC column exit, 11, 12, 14, 82
- peculiarities compared with molecular transportation

- - efficiency for short-lived nuclides, 84
- - spike profile change with distance, 83

B

Bayesian statistics, 197, 202, 203, 209. See also Poor-statistics data, Bayesian treatment

Bayesian (confidence) intervals, BI, 197
Bis for difference of Poisson-distributed quantities (table), 200
Bis for ratio of Poisson-distributed
- quantities, (table), 200, 201
- compared with frequentist statistics, 197
- likelihood function, 197, 198, 202, 203, 209
- posterior distribution of parameter, 197, 198
- prior distribution of parameter, 197, 198
- complete ignorance of, 198, 199
- statistical inference, 197
Bimolecular reactions, 67, 186
- rate of, 37-39
Bohrium (Bh, element 107), 12
- longest-lived isotopes, 55
- volatile oxychloride, 12
Boltzmann factor, 42, 100, 136, 160, 161
- integrals containing the factor, 42, 43
Brominating agents. See Synthesis of volatile compounds on-line.

C

Carrier gas (definition), xxii
- hold-up time of. See Gas hold-up time

Chemical identification of TAEs (definition), xviii

Chemisorption, 119, 120, 153, 172, 181
Chemical volatilization, xxi, 75
Chlorinating agents. See Synthesis of volatile compounds on-line.
Chlorination of adsorbed tracers, 70-72
- conditions for fast kinetics of, 71
- Zr with TiCU -* ZrCU on silica surface, 70-72
Chlorination of gaseous tracers. See also Synthesis of volatile compounds on-line; Scavenging impurities in carrier gas

- bimolecular steps involving radicals, 65
- - activation energy versus enthalpy change, 67
- conditions for fast kinetics of, 66, 67, 71, 72
- mechanism of Zr with TiCU - * ZrCU, 65
- thermochemistry and kinetics, 65
- thermochemistry of all possible reaction paths

- - Zr with TiCl₄ -> ZrCl₄ , 67-69
- - Zr with SOCl₄ -> ZrCl₄ , 68
- - W(Mo) with SOCl₄ -> W(Mo)OCl₄ , 69, 70
Chlorination on hot aerosol filters, 72
Chromathermography, 97, 112
Chromatographic peak shape, 93-100
- statistical moments and cumulants, 93, 94
Chromatographic peaks in IC

- approximate profile formula, 97
- computer simulations. See Monte Carlo simulations

- dispersion due to

- - laminar flow patterns, 95
- - longitudinal diffusion, 95
- - migration slower than flow velocity, 95
Chromatographic peaks in TC
- approximate formulae for slow flow, 99, 100
- compression by temperature gradient, 97, 98
- computer simulations. See Monte Carlo simulations

- dispersion at very low flow rates, 97-100

- fitting by exponentially modified Gaussian, 108-110
Collisions of molecules. See Molecular kinetics

Cunningham slip correction, 44

D

De Broglie wave length, 129
Desorption energy (definition) 165, 166
Desorption energy data by Third Law: heterogeneous surface, localized adsorption

- exceeds sublimation energy, 140, 141, 177, 178. Cf. Adsorption enthalpy (experimental) by Third Law

- possible factors enhancing high values of, 175
- - adsorption pockets, 173, 174
- - incomplete modification of surface, 176, 177
- - localized rather than mobile adsorption, 173, 174
- - losses of internal entropy in adsorption, 174
- uncertainty of some required quantities, 174, 175
Desorption energy, heterogeneous surface fundamentals, 167-169. See also Adsorption enthalpy

- spectra of, 167
- spectra of, assumed for discussion, 168, 169
- - effective mean value of energy, 168
- - Second Law treatment of effective energies, 168, 169
- spectra calculated by molecular dynamics, 176
Desorption entropy, heterogeneous surface. See also Adsorption entropy

- accounting for surface diffusion, 169-171
Detection of rare decay events of heavy elements

- ionization chamber for fission events, 17
- semiconductor detectors of a particles and fission fragments, 12, 15
- solid state track detectors of fission fragments, 6
Diffusion. See Aerosols, diffusion coefficient; Diffusional deposition in channels; Gaseousdiffusion; Knudsen diffusion; Surface diffusion

Diffusional (irreversible) deposition in channels deposit density and penetration - analytical solutions for diffusionally developing laminar flow

- - for circular channels, 46, 47

- - for rectangular channels, 47, 48

- engineering approach, 48

- - for developed turbulent flow, 50
- - for diffusionally and hydrodynamically developing, laminar flow, 49, 50
Dubnium (Db, element 105), 12, 13, 73
- bromides of, 13
- chlorides of, 192
- longest-lived isotopes, 55

E

Ekahafnium. 7, 202. See Rutherfordium

Element 112 (Ekamercury)
- adsorption on gold, 17
- longest-lived isotopes, 55
- volatility in atomic state, 16
Engeworth-Cramer asymptotic expansion, 94
Entropy. See Adsorption entropy; Partition functions

Exponentially modified Gaussian, 94, 95
- fitted by Gram-Charlier series, 95
- fitting Monte Carlo simulations by, 107-110
Elution curve, 63, 64, 82, 83, 87, 88, 93, 96, 124

F

Fluorinating agents, 22
Free random
- displacements in VTC column, 114, 116
- flights in gas, 101, 102
- jumps in surface diffusion, 161
Future research needs
- advanced peak profile simulations, 112
- conditioning of open columns, 179
- formulae for thermochromatographic peaks, 98, 100
- more of precise comparative data for known elements, 177, 178, 180

G

Gas hold-up time, 20, 38, 53, 62, 63, 70, 75, 84, 91-93, 101, 202
Gaseous diffusion, 40
- as a result of random flights, 41
- coefficient of mutual diffusion, 40, 41, 45, 77, 96

- - for two-dimensional gas, 173
- Gilliland equation for the coefficient, 40
Gas-solid chromatography method and experimental techniques. See Chromathermography; Isothermal chromatography (IC); Temperature programmed chromatography; Thermochromatography (TC)

- non-trivial chromatographic mechanisms. See Reaction chromatography
- realization of, on-line with accelerator beams

- - advantages and disadvantages of TC and IC for transactinoid studies, 13, 14

- first on-line experiments with Hf and Rf, 5

- simulation of, using fission products, 4
Gram-Charlier series, 94

H

Hassium (Hs, element 108), 14-16
- longest-lived isotopes, 55
- volatile tetroxide of, 14-16, 178, 209
Heterogeneous surface. See Desorption energy; Desorption entropy; Surface of fused silica; Surface of metals

I

Internal chromatograms, 87, 88, 90
- in isothermal chromatography, 87
- in thermochromatography, 87, 88, 90, 105
Isothermal chromatography (IC). See also Reaction chromatography

- characteristic of the method, 87, 88
- theory of ideal, 89-91
- - gas hold-up time, 90
- - migration distance, 90
- - net retention time, 90, 103

K

Knudsen diffusion (regime) in evacuated channels, 112
- description by effective flow, 112
- effective diffusion coefficient, 114, 115
- Monte Carlo simulation by random flights, 116, 117

L

Lanthanoids (definition), xxiii
Lateral diffusion (migration) of adsorbate. See Surface diffusion

Localized adsorption model. See Adsorption entropy

Loschmidt number, 36

M

Mobile adsorption model. See Adsorption entropy

Molecular kinetics, 36-43
- collisions of gaseous molecules, 38, 39
- - collision diameter, 39, 40
- - rate of chemical interaction, 37-39
- - reduced mass of colliding particles, 38
- collisions of gaseous molecules with walls, 37
- - number of, when passing a volume, 38
- concentration of gaseous molecules, 36, 37
- mean speed of gaseous molecules, 37
Monte Carlo simulations of experimental data on few atoms. See Poor-statistics data, Bayesian treatment.
Monte Carlo simulations of likelihood function. See Poor-statistics data, Bayesian treatment.
Monte Carlo simulations of molecular migration histories and chromatograms

- assumptions and approximations, 101-104, 110, 111
- individual paths in time and distance, 104
- microscopic picture of migrations, 100, 101
- migration distance as sum of long jumps, 102
- - effective long jumps (exponential pdf), 103
- - jumps of zero length, number of, 102, 103
- - simplified pdf of displacements, 101-103
- retention time as sum of multiple sojourns at jump endpoints, 103-105
- - pdf of the sum, 103
- simulation flowchart, 106
- - graph of simulated individual paths, 104
- simulations of internal chromatograms, examples

- - elution TC, long-lived nuclide, 109
- - elution TC, short-lived nuclide, 109

- - frontal TC, long-lived nuclide, 109

- - fits of peaks with exponentially modified Gaussian, 109, 110
- - statistical characteristics of simulated and fitting peaks, 110, 111
- variables affecting peak shapes, 110-111

N

Net retention time. See isothermal chromatography, theory; Thermochromatography, theory

P

Partition functions, molecular, molar, 128, 129
- rotational, 130
- translational, 129, 130
- - for two-dimensional gas, 129
- vibrational, 130
Peclet number (Pe), 96
Physical adsorption,
- adsorption sojourn time, 42, 88, 89, 101, 108, 172, 173, 180
- elementary adsorption-desorption event, xix, 42, 90, 102, 111, 120, 165, 180
- London dispersion forces, 120
- vibrations of adsorbent lattice, 42, 161, 180
Physisorption. See Physical adsorption

Poisson distribution, computer simulation, 207
Poor-statistics data, Bayesian treatment. See also Bayesian statistics

- adsorption enthalpy from corrupted thermochromatogram, 209-211
- - persisting ambiguities, 210, 211
- adsorption enthalpy from IC data, 204-208
- - evaluation of survival rates, 205, 206

- - formulae for survival yield, 204

- - likelihood function by Monte Carlo, 207

- - uncertainty of final data, 208

- adsorption enthalpy from TC experiment basic formulae, 208, 209
- half-life from incomplete decay curve, 202, 203
- - likelihood function by Monte Carlo, 203
- - sketch of flowchart, 203
Production of transactinoids, 54, 55
- actinoid targets, 54
- effective production cross section, 54, 55
- evaporation residues

- - recoil energy and range in target material, 56
- - straggling of recoil range, 56
- heavy ion beams (C to Ca), 54
- - available intensities, 54, 55, 57
- - optimal energy, 55
- simultaneous production of chemical homologs, 57

R

Random flights, 40, 100, 112, 114-116
Reaction chromatography, 180-181
- associative adsorption - dissociative desorption, 183
- - atomic silver silver chloride, 183
- dissociative adsorption - associative desorption, 181-183

- - (Ce, Pu, Bk)Cl₄ (Ce,- Pu, Bk)Cl₃ , 181, 182
- - complexes with Al₂Cl₆, 182, 183
- - Mo and W oxide-hydroxides, 182
- physical adsorption - substitutive desorption, 184-186
- - W and Sg oxychlorides, 184-186
- substitutive adsorption - substitutive desorption, 183-184

- - (Zr, Hf, Rf)Cl₄ (Zr, Hf, Rf)Cl₄, 183
Reference states for mobile and localized adsorption, 162
Retention time, 90, 91, 103, 105, 124, 136, 181
- in vacuum thermochromatography, 112
- measurement of, 5, 10, 12, 28, 62-64
Reynolds number (Re), 48-50
Roughness of surfaces, 141, 142
- indices of, 142
- of fused silica, experimental data, 142-146
- of metals, 158
- reduction of, by chemical etching, 158,
Rutherfordium (Rf, element 104), 6-8

- longest-lived isotopes, 55
- oxychloride and tetrachloride of, 12, 183

S

Scavenging impurities in carrier gas, 73
- deposition of nonvolatile and aerosol species. See also Diffusional deposition - - calculated graphs of deposit density and penetration (laminar flow), 75-77
- - turbulent flow, formulae and data, 77, 78
- removing interfering radionuclides by hot CaO and Si0₂ filters, 74, 75
- removing water with SOCl₂ or BBrt, thermodynamics and mechanism, 73, 74
Schmidt number (Sc), 48-50
Seaborgium (Sg, element 106), 8, 9,
- longest-lived isotopes, 55
- oxide hydroxides of, 182
- oxychlorides of, 9, 69, 70, 184, 204, 209
Separations of groups of related elements,

- elements of groups 7 to 10, 27, 28
- homologs of elements 112 to 117, 27-29

- fission products, 28-30

- lanthanoids and actinoids, 24, 26, 27
Sherwood number (Sh), 48-50
Single atom chemistry, validity of, 191-196.See also Poor-statistics data, treatment

- fluctuation of a system property with number of entities, 195
- kinetic limits for exchange of ligands, 194
- probability equivalent to law of mass action, 194, 195
- supported by Monte Carlo simulations of TC experiments, 192, 193
- verified by coprecipitation of Po from solutions, 192
Sizes of ions (atoms) in compounds, 140
- based on additive crystal radii, 140
- visualization of relative, 139, 141, 150, 152
Standard states, xxii, 133. See also Adsorption thermodynamics

Stirling's series and approximation, 195, 196
Superheavy nuclides / elements (definition), xxiii

- atomic electronic ground state, xxiii

- chemical character, xxiv

Surface diffusion on homogeneous surface, 159-162
- as two-dimensional Brownian motion, 161
- diffusion (migration) barrier, 159-162,
- distribution and mean of stochastic jumps, 160, 161
- effective diffusion coefficient, 161
- history of the problem, 159
- observation of atomic jumps, 161
- random migration picture of, 160
Surface of fused silica, bare. See also Surface of fused silica, hydroxylated; Surface of fused silica, modified

- calculated energy potential, 146-148
- calculated adsorption potential for N₂, 148
- heterogeneity (at atomic level)

- - distortion of SiO₄-network, holes between the tetrahedra, 146, 147
- - strained two and three membered rings, 151, 152
Surface of fused silica, hydroxylated

- dehydratation, 150, 154
- dehydroxylation, 149-151, 153, 154, 157
- hydratation, 154
- hydroxylation, 148-150
- rehydroxylation, 153-155
- silanols, 148, 149, 151-157, 172, 176, 177, 179
- - geminal, isolated, vicinal, 149
- - position in nanoscale structures, 151, 152
- siloxanes, 148, 151, 154, 155, 157, 172, 177
Surface of fused silica, modified, 155
- microscopic picture of, 171, 172
- by various agents, 156, 157,
- by SOCl₂ , 156
- by TiCU, 155, 156
Surface of metals, 157-159,
- modification by reagents, 158, 159
- - nickel modified with bromine, 159
- morphology of bare, 157
- - kinks, steps, terraces, 157
- roughness reduction, 158
- - by ion bombardment plus annealing, 158
- - by polishing, 158
Synthesis of volatile compounds on-line.See also Chlorination of gaseous tracers

- brominating agents, 21, 73, 155
- chlorinating agents, 3-6, 20, 21, 60-73, 155, 182, 183, 186
- experimental evidence for fast synthesis

- - of ZrCl₄ from fission product Zr, 61
- - of HfCl₄ from heavy ion produced Hf, 62-64
- in-situ volatilization, xviii, 4, 5, 16, 54, 72-74

T

Temperature-programmed chromatography,

- of fission product chlorides, 30
- of lanthanoid complexes with Al₂Cl₆, 26
- of oxides, 19
Thermal diffusivity, 78, 79
Thermalizing nuclei recoiling from target

- carrier gas under heavy ion beam

- - concentration of ions in gas, 58, 59
- - energy absorption rate, cm³ s^-1, 58
- - LET and range of heavy ions, 57, 58
- optimal size of target chamber, 56, 57
- range of recoiling evaporation residues, 57
Thermochromatographic columns, 15, 78, 142, 143
- equal temperature of gas and wall, 78
- temperature profile, 3, 88, 97, 111, 116, 137
- - measurement of true, 78
Thermochromatography (TC), xvii, xxii. See also Reaction chromatography characteristics of method, 87-89
- internal chromatograms in, 87, 88, 90, 105
- net retention and gas hold-up times, 91-93, 136
- - at constant column temperature gradient, 92
- - at exponential temperature profile, 92
- theory of ideal, 91-93, 208
Thermodynamic and thermochemical
- properties of (oxy)halides of present interest compounds of B, 73, 175
- compounds of Ti, 69-69, 71, 74, 175
- compounds of W, 69, 70
- compounds of Zr, 68, 71, 72, 174, 175
- of SOCl₂ and its decomposition products, 68
Tracer (definition), xxi
Transactinoid elements. See also Production of transactinoids

- definition, xxiii
- electronic structure of atomic ground state, xxiii

- longest-lived isotopes, 55
- names and symbols for, xxiv

Trouton's rule, 2, 138

U

Unknown compounds, general, xviii, 187
- (oxy)fluorides of Np to Es, 22
Uranium impurities in detectors, 6, 7

V

Vacuum thermochromatography VCT, 112-117
- non-rigorous definition, 112
- description by random flights, 114
- - equivalent diffusion coefficient, 114, 115
- - mean lengths and dispersion of flights, 114
- isothermal separation impossible, 112
- Knudsen regime, 112-115
- - cosine law, 116
- - correct computer simulation, 116
- retention time versus adsorption enthalpy, 113
- - using vacuum conductance as effective convective flow, 113
- - considering linear diffusion with decreasing coefficient, 115, 116
- simulation of, by Monte Carlo, 116, 117

Van't Hoff equation, 124, 169

Volatile compounds of heavy elements early use in radiochemistry, xvii, xviii

- complexes with Al₂Cl₆, 25-27
- halides and oxyhalides, 21, 22
- metals, 18, 24
- oxides and oxide hydroxides, 18
- sulfides, 20
- structural reasons for enhanced volatility, 2, 20, 23, 25

Z

Zone profile.See Chromatographic peaks, shapes

Autor

Ivo Zvára

Joint Institute for Nuclear Research
Dubna
Russian Federation

Reviews

From the reviews: "This is an interesting and well-prepared book. ... it covers, only the gas-phase chemistry of elements of atomic numbers greater than Z = 103. As a result, it will be of interest to ... readers of JACS. ... In the six brief chapters, the limited data are well evaluated and presented." (Gregory R. Choppin, Journal of the American Chemical Society, Vol. 130 (42), 2008)