lesson 15 the transuranium elements. the basics 118 known elements, 1-118 all elements beyond 92...
TRANSCRIPT
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Lesson 15
The Transuranium Elements
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The Basics
• 118 known elements, 1-118• All elements beyond 92 man-made
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Modern Periodic Table
New element names/symbols 114=Fl=Flerovium116=Lv=Livermorium
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The history of the periodic table
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The periodic table, circa 1940
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Making new elements by simple reactions
• The first man-made transuranium element, neptunium, Z=93
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Making new elements by simple reactions (cont.)
• The second man-made transuranium element, plutonium, Z=94
The announcement of the discovery of Pu
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Making new elements by simple reactions—the role of chemistry
• The discovery of elements 95(Am) and 96 (Cm)
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Making new elements with nuclear weapons
• The synthesis of elements 99 (Md) and 100 (Fm)
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MIKE
Samples of the bomb debris were collected on filter papers by aircraft flying through the mushroom cloud
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Using heavy ion reactions to make new elements—The
Berkeley era
Albert Ghiorso Glenn Seaborg
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Synthesis of elements 101-106
• Making elements one atom at a time• 254Es + 4He256Md + n
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The problem
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The Solution—The Darmstadt Era
• “Cold Fusion” Reactions• Bombard Pb or Bi with heavy ions—
the resulting species are borne “cold” –with low excitation energies—they survive better
Peter Armbruster Sigurd HofmannYuri Oganessian
Gottfried Munzenberg
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The end of the “cold fusion” path
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“Hot fusion-The Dubna Era”
Yuri Oganessian
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History of Heavy Element Discoveries
• G.T. Seaborg and W. Loveland, The Elements Beyond Uranium
• S. Hofmann, On Beyond Uranium
• The textbook
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The limits of the periodic table
• Can this go on forever? NO!!• Nature puts a limit on the size of
the periodic table, related to the relative strength of the electromagnetic and nuclear forces.
• The limit is about 125 elements.
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The End of Chemistry
• Does the Periodic Table have limits? YES!!
• At some point (Z~122) all the electron energy levels of adjacent elements are similar so that there are no differences in their chemical behaviour.
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Superheavy elements
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Why are the “inert” gases inert?
• They have full shells of electrons• Full electron shells stability• Important exception: A professor
at UBC discovered many years ago that Xe could form chemical compounds with the very reactive element F.
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Are there nuclei with special stability?
• Nuclei with full shells of neutrons and protons.
• Shell model of the nucleus• Special stability associated with
2,8,20, 28, 50,82, 126 neutrons or protons. (These are called the “magic numbers”)
• Where is the next proton magic number?
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The “Island of Stability”
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Superheavy elements
• The allegorical picture has stuck even though it is wrong. There is no “island of stability”
• “superheavy” = “shell-stabilized”
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Current view
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Methods of Heavy Element Synthesis
• Cold fusionPb, Bi as targetMassive ProjectileE*~ 13 MeV, high
survivalBig fusion hindranceUsed to synthesize
107-113
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Methods of Heavy Element Synthesis
• Hot fusionReaction of lighter
projectile with actinide target
Low fusion hindrance
High E* (30-50 MeV), low survival
Used to synthesize 102-106, 113-118
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How do you make heavy nuclei?
• Starting material• The latest synthesis of a chemical
element was the synthesis of element 117 via the reaction 249Bk(48Ca, 3n)294117.
• The two-year experimental campaign began with a 250-day irradiation in HFIR, producing 22 milligrams of berkelium-249, which has a 320-day half-life. The irradiation was followed by 90 days of processing at REDC to separate and purify the berkelium. The Bk-249 target was prepared at Dimitrovgrad and then bombarded for 150 days at the Dubna facility.
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How do you make heavy nuclei?
• Particle accelerators
• Intense particle beams are needed. Cross sections are ~picobarns, which means one makes 1 atom per week. Cross sections as low as 32 femtobarns have been studied (1 atom/year)
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How do you make heavy nuclei?
• Separators
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Production of Heavy Elements in Complete Fusion Reactions
• We need to know three spin-dependent quantities: (a) the capture cross section, (b) the fusion probability and (c) the survival probability, and their isospin dependence
where
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How well can we describe observations?
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Let’s look at this more carefully
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Despite correctly predicting σEVR correctly, ,
the values of PCN (and Wsur )differ significantly
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Conclusions
• For the 50-150 “calibration” reactions, we know capture cross sections within 50%
• We know interaction barriers within 20%• For the heavy element synthesis
reactions, we know the capture cross sections within a factor of 2.
• The “coupled channels” calculations (such as Zagrebaev) do the best overall job of describing capture cross sections.
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What about Wsur?
• Well-established formalism for calculations
• Principal uncertainty is the values of the fission barrier heights.
• Best calculations for SHE show an average discrepancy between data and theory to be 0.4 MeV, with largest error being 1.0 MeV.
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Γn/Γf evaluated from Vandenbosch and Huizenga expression
)1/2
fB*
CNE
1/2
nB*
CNE1/2exp(2a
11/22ak
)nB*
CN(E2/34A
)*CN
(EfΓ
)*CN
(EnΓ
2/1*fCN BE
k=9.8 MeV a=A/12 MeV-1
Bn, Bf from Möller et al., (ADNDT 39,213; 59, 185)
xi
iEifn
nxnsur EPW
max
1*,
*)(
Calculation of Wsur
Collective enhancement of the level densityDeformation dependence of the collective enhancementEnergy dependence of the collective enhancement
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How well can we calculate Wsur?
• We took a group (~75 ) heavy element synthesis reactions where Z1Z2 < 1000 (ZCN =98-108) and compared the calculated and measured values of σEVR.
• The average ratio of (measured/calculated) cross sections was 6.5. We conclude that we know Wsur within a factor of 3.
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What about PCN?
• This is the most difficult quantity to estimate or measure.
• There are a limited number of measurements of PCN.
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Excitation Energy Dependence of PCN
)(
exp1
)*,(*int
*
0
JEE
PJEP
B
CNCN
Zagrebaev and Greiner
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PCN (E*)
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PCN (fissility)
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Hot fusion systematics
E*=35 MeV
48Ca + X
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Hot fusion predictions
• 249Bk(48Ca,3n)294117 σEVR=1 pb.
• 249Bk(50Ti,4n)295119 σEVR=0.07 pb.
• 248Cm(54Cr,4n)302120 σEVR=0.02 pb.
• 244Pu(58Fe,4n)302120 σEVR=0.006 pb.
• 238U(64Ni,3n)302120 σEVR=0.004 pb.
Based upon MNMS masses
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Chemistry of the Heaviest Elements
• Relativistic Effects important since electron velocities approach that of the speed of light.
• Must use Dirac equation rather than the Schrodinger equation.
• Already known in Au, etc.
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Relativistic Effects in Atomic Physics and Chemistry
• In high Z atoms. speed of inner electrons approaches c, mass of electron increases. Radius of orbits contracts.
For Sg, =0.77, a/a0=0.64
This defines the “direct relativistic effect” , ie. contraction of s and p1/2 orbitals
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Direct Relativistic Effect
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“Indirect” Relativistic Effect
• Due to contraction of s and p1/2 orbitals, outer electrons are more effectively screened and outer p,d,f orbitals expand.
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Spin-Orbit Splitting
• Levels with > 0, are split into
and
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Effect of This
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The “new” Aufbau diagram
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Au--and heavier elements
• Contraction of 6s, expansion of 5p orbitals reduces the energy difference between these orbitals to that of a photon of blue light-> Au absorbs blue light and appears yellow.
• Non-relativistic -> Au would be unable to absorb light
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Chemistry Apparatus
• Rapid chemistry• Both gas and
liquid systems• Chemistry
separate from production.
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Chemistry Apparatus
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Chemistry of Element 112
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Chemistry of element 114
• 3 events observed at Dubna by PSI group, corresponding to 287114, 288114, and 289114 from 48Ca + 242,244Pu. (Eichler et al, Radiochimica Acta 98, 133 (2010)). Conclude that element 114 seems to behave like a very volatile metal, with very weak interaction with Au – even weaker than element 112. Most likely gaseous at ambient temperatures.
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Chemistry of element 114
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More prosaic, yet vexing chemistry, Rf-Hs• Rf
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Db
• Expts. complicated and difficult
• Not well understood
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Sg
• “Normal” behavior
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Bh
• “the chemistry of bohrium is boring”
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Hs
• Chemistry at the 1 pb level
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Environmental chemistry of the
transuranium elements
• Plutonium is the most important element.
• Present due to atmospheric testing, satellite re-entry and nuclear power accidents
• Extremely low concentrations (~10-
18M)• Low levels in soil, sediments, etc.
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Aqueous environmental chemistry of Pu
• Hydrolysis• Complexation, redox reactions,
colloid formation also important.
• Hydrolyic seriesAn4+>AnO2
2+> An3+> AnO2+
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Complexation