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The Ionic Radius of No A. Bilewicz Department of Radiochemistry, Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-1

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The Ionic Radius of No A. Bilewicz Department of Radiochemistry, Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-1 Journal of Nuclear and Radiochemical Sciences, Vol.3, No.1, pp. 147-149, 2002 147 The Ionic Radius of No A. Bilewicz Department of Radiochemistry, Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw, Poland Received: November 13, 2001; In Final Form: April 30, 2002 Nobelium (No, T1/2=58 min) was produced in bombardment of Cm target with 18O5+ ions. Next, it was oxi- dised by H5IO6 and loaded together with lanthanide tracers on a chromatographic column filled with cryptomelane MnO2. In the HNO3 elution curve two peaks are observed. First one is related to the nonoxidized No2+ and the second corresponds to No3+ close to positions of elution peaks of Ho3+ and Y3+. The ionic radius deduced from the elution position of No3+ is to be 89.4•}0.7 pm. 1. Introduction to possess interesting ion exchange properties. The cryptome lane MnO2 phase has a well-defined 2•~2 tunnel-framed struc Studies of the heaviest actinides and comparison with the ture with exchangeable hydrogen, alkali, or alkali earth cations.6 properties of lanthanides are interesting because they help to The presence of exchangeable ions in the tunnels requires that understand the influence of relativistic effects on the chemical some of the manganese atoms must be present in oxidation properties. The relativistic effects influence the contraction of states lower than 4. The formulae could be represented by the 3+ lanthanides and actinides ionic radii by two ways: split- HMnIV7 MnIII O16 as postulated by Tsuji and Tamaura. The av ting of outermost p orbitals and stabilization of p1/2 orbitals, and erage tunnel diameter is 0.28 nm so the selectivity of the sor expanding the f5/2 and f7/2 orbitals which results in less effective bent is related to the stenc effect in the tunnel structure. Cryp shielding of the nuclear charge. For the heaviest actinides these tomelane MnO2 has been demonstrated to show excellent ion- might result in ionic radii different from non-relativistic extrap- exchange selectivity towards cations with crystal ionic radii of olations. For example, in the case of Fm3+ the relativistic effect 130-150 pm, e.g. K+, NH+4, Ba2+, and Ra2+ (Ref. 6-8). For 3+ is responsible for 8 pm contraction of the ionic radius, while for lanthanides and actinides the distribution coefficients are much Er3+ only 2.5 pm. The determination of the ionic radius of No3+ lower, but strongly depend on the radius of cations. Addition- ion is of key interest, particularly since the ionic radius of Lr3+ ally, in acidic solutions the sorbent exhibits both ion exchange has been determined. This measurement would conclude the and strong oxidizing properties, so No3+ should be stabilized in ionic radius determinations of the 3+ actinide ions. cryptomelane MnO2 phase. In the present work, cryptomelane The ground state electronic configuration of nobelium is type MnO2 is used for the determination of No3+ ionic radius by [Rn]5f147s2. Energy of 5f7/2 orbitals in nobelium (-15.43eV) chromatographic methods. is more negative than 4f7/2 orbitals in ytterbium (-14.67 eV) (homologue in lanthanide series) which causes that nobelium 2. Experimental as the only one among f electron cations is very stable in the oxidation state 2+. The redox potential of the No2+/No3+ cou 2.1. Synthesis of Cryptomelane Manganese Dioxide. Manganese dioxide samples were synthesized according to the ple was determined to be 1.4•}0.2 V. This aspect of nobelium chemistry provides special problems for the determination of the procedure used by Tsuji and Abe. The precipitates were ob No3+ ionic radius. In the determination experiment first No2+ tained by adding 250 cm3 of 0.5 M KMnO4 in 1 M H2SO4 must be oxidized to the No3+. This can be accomplished with to 250 cm3 of 1 M MnSO4 solution containing 1 M of H2SO4 the use of strong oxidizing agent such as KMnO4 (1.5 V) or at 60•Ž. The precipitates were then aged overnight, filtered, H5IO6 (1.7 V). The second problem is to stabilize in the 3+ ox and washed with water. The product was dried at ca 70•Ž for idation state during the determination experiment. three days, and then ground and sieved. The samples were trans- Ionic radii are usually obtained from X-ray diffraction data formed to the H+ form by percolating 6 M HNO3 solution. for oxides or fluorides. However, these techniques require 2.2. Radioactive Tracers. The radionuclides of Sr, Ca, weighable quantities of the compound. Unfortunately, elements Y, Lu, Yb, Tm, Ho, Eu, and Am were pur- heavier than fermium are produced in quantities of few atoms chased from Isotope Products in Swierk, Poland. All tracers at a time, so that experimental structural data for these elements were stored in 6 M HNO3 solutions to prevent them from hy are not available. The values of ionic radii for Md2+, Md3+, drolysis. No2+, and Lr3+ were determined only by chromatographic meth- 2.3. Production of No. The No (T1/2=58 min) atoms ods. The ionic radii of Md3+ and Lr3+ were determined by were obtained by O irradiation of Cm target in reaction: comparing their elution positions with the positions of rare earth 248Cm(O tracers and of actinides of known ionic radii. The ionic radii of , ƒ¿3n)No. (1) Md2+ and No2+ were determined by comparison with crystallo- The experiments were carried out at Philips cyclotron at the graphic radii of Ca2+, Sr2+, and Ba2+ (Ref. 3, 4). For the determination of ionic radius of No3+, Henderson5 Paul Scherrer Institute, Villigen (Switzerland). Target of used ion exchange chromatography with KMnO4 and H5IO6 as 0.730 mg.cm-2 Cm was irradiated for 2.5 h with O ions. oxidizing agents and ƒ¿-HIB as eluent. Unfortunately, these The beam energy on target was 99 MeV, and the beam intensity strong oxidants decomposed both the ƒ¿-HIB and the ion ex- was 1 x 1012particles per second. Under these conditions, No change resin and, therefore, the determination of No3+ ionic ra is produced with the cross section of about 30 nb. The target dius could not be accomplished using this approach. contained 10% of Gd thus producing simultaneously In our laboratory, samples of cryptomelane-type MnO2 inor and 165. The reaction products recoiling out from the target were stopped in He gas and transported to the chemistry collec ganic ion exchanger were synthesized. This sorbent is known tion site by a KCl aerosol-seeded gas jet system. The aerosol E-mail: [email protected]: ++48 228111532. with reaction products was collected on a glass filter. (c) 2002 The Japan Society of Nuclear and Radiochemical Sciences Published on Web 6/30/2002 148 J.Nucl.Radiochem.Sci.,Vol.3, No.1, 2002 Bilewicz Figure 3. Sum of the elution curves from the experiments where No was detected. chromatographic system is defined as: Figure 1. Dependence of logarithm of distribution coefficient on re ciprocal crystal ionic radius for lanthanides, yttrium, and americium. Kd=Vm-Vf/Vs (2) where Vm and Vs are the volumes of the mobile and the station 2.4. Chromatographic Procedure. A small glass column ary phase, respectively, and Vf is the free column volume. (3 mm•~5 cm) was filled with 0.5 g cryptomelane MnO2 (0.01- 0.05 mm) and preconditioned with solution of HNO3. The lan- 3. Results thanides and americium tracers were dissolved in 0.5 M HNO3, evaporated, and dissolved in 20 ƒÊL of 0.5 M HNO3 and 0.05 M The selectivity for the cations on cryptomelane MnO2 H5IO6. Next, the solution was placed on the top of the column. strongly depends on the ionic radii of the exchanged cations. The radionuclides were subsequently eluted from the column Because the diameter of the tunnel in the MnO2phase (280 pm) with 0.5 M HNO3 solution at a flow rate of 0.1 cm3 min-1. Drop is similar to diameters of the metal cations, the selectivityof the fractions from the column were collected and measured by ƒÁ sorbent is associated with the steric effect. The hydrated 3+ spectrometry or by liquid scintillation counting (Ca, Y). metal cations with diameter much larger than 280 pm must be dehydratedbefore entering the ion exchange phase. Therefore, The same chromatographic procedure was used in nobelium the selectivity of the cyptomelane MnO2 depends linearly on experiments. The aerosol, together with the reaction products, free energy of hydration, which is also linearly related to the was dissolved in 2 cm3 of 0.5 M HNO3, evaporated, and dis- reciprocalof crystal ionic radius. The linearity of log Kdon ionic solved in 20 ƒÊL of 0.5 M HNO3 and 0.05 M H5IO6. The drops radii for f electroncations was also found by Tsuji et al. There from the column were collected on stainless steel disc and evap are numerousdata for ionic radii of the cations. The values com orated on a hot plate. After evaporation the samples were in monly used are Shannon radii. In case of heaviest actinides serted into the detector array for a spectroscopy, consisting 6 (Es3+,Fm3+, Md3+,and Lr3+)all available experimental ionic Si(Au)-surface barrier detectors, for 2.5 h measurement. The radii are given in the Templetonand Dauben scale. In order a events, together with the detector numbers and the associ to allow comparison we also used the Templeton and Dauben ated time, were recorded. Spontaneous fission events were also scale to present the ionic radii of the lanthanides and actinides recorded. Before a measurement the y activity was measured by cations studied.
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