Lecture 1: RDCH 710 Introduction
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Transcript Lecture 1: RDCH 710 Introduction
CHEM 312: Lecture 15 Americium and Curium
Chemistry Part 1
• Readings: Am and Cm
chemistry chapters
Link on web page
• Combined due to similar
chemical properties of elements
Cover Am then Cm
• Nuclear properties
• Production of isotopes
• Separation and purification
• Metallic state
• Compounds
• Solution chemistry
• Coordination chemistry
15-1
Production of Am isotopes
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Am produced in reactors from neutron irradiation of Pu
239Pu to 240Pu to 241Pu, then beta decay of 241Pu
241,243Am main isotopes of interest
Long half-lives
Produced in kilogram quantity
Chemical studies
Both isotopes produced in reactor
241Am
source for low energy gamma and alpha
Alpha energy 5.44 MeV and 5.49 MeV
Smoke detectors
Neutron sources
(a,n) on Be
Thickness gauging and density
242Cm production from thermal neutron capture
243Am
Irradiation of 242Pu, beta decay of 243Pu
Critical mass
242Am in solution
23 g at 5 g/L
Requires isotopic separation
15-2
Am solution chemistry
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Oxidation states III-VI in solution
Am(III,V) stable in dilute acid
Am(V, VI) form dioxo cations
Am(II)
Unstable, unlike some lanthanides (Yb, Eu, Sm)
Formed from pulse radiolysis
* Absorbance at 313 nm
* T1/2 of oxidation state 5E-6 seconds
Am(III)
Easy to prepare (metal dissolved in acid, AmO2
dissolution)
Pink in mineral acids, yellow in HClO4
when Am is 0.1 M
7
5
F0 L6 at 503.2 nm (e=410 L mol cm-1)
Shifts in band position and molar absorbance
indicates changes in water or ligand coordination
9 to 11 inner sphere waters
Based on fluorescence spectroscopy
* Lifetime related to coordination
nH2O=(x/t)-y
x=2.56E-7 s, y=1.43
Measurement of fluorescence
lifetime in H2O and D2O
Am(IV)
Requires complexation to stabilize
dissolving Am(OH)4 in NH4F
Phosphoric or pyrophosphate (P2O74-)
solution with anodic oxidation
Ag3PO4 and (NH4)4S2O8
Carbonate solution with electrolytic
oxidation
15-3
Am solution chemistry
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Am(V)
Oxidation of Am(III) in near neutral
solution
Ozone, hypochlorate (ClO-),
peroxydisulfate
Reduction of Am(VI) with bromide
5
I43G5; 513.7 nm; 45 L mol cm-1
5I 3I ; 716.7 nm; 60 L mol cm-1
4
7
Am(VI)
Oxidation of Am(III) with S2O82- or Ag2+
in dilute non-reducing acid (i.e., sulfuric)
Ce(IV) oxidizes IV to VI, but not III to VI
completely
2 M carbonate and ozone or oxidation at
1.3 V
996 nm; 100 L mol cm-1
Smaller absorbance at 666 nm
Am(VII)
3-4 M NaOH, mM Am(VI) near 0 °C
Gamma2-irradiation 3 M NaOH with N2O
or S2O8 saturated solution
Am(VII)
Broad absorbance at 740 nm
15-4
Am solution chemistry
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Am(III) luminescence
7F 5L at 503 nm
0
6
Then conversion to
other excited state
Emission to 7FJ
5D 7F at 685 nm
1
1
5
7
D1 F2 at 836 nm
Lifetime for aquo ion is
20 ns
155 ns in D2O
Emission and lifetime
changes with speciation
Am triscarbonate
lifetime = 34.5 ns,
emission at 693 nm
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Autoreduction
Formation of H2O2 and HO2 radicals from
radiation reduces Am to trivalent states
Difference
between 241Am and
243Am
Rate decreases with increase acid for
perchloric and sulfuric
Some disagreement role of Am
concentration
Concentration of Am total or
oxidation state
Rates of reduction dependent upon
Acid, acid concentration,
mechanism
Am(VI) to Am(III) can go
stepwise
starting ion
Am(V) slower than Am(VI)
15-5
Am solution chemistry
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Disproportionation
Am(IV)
In nitric and perchloric acid
Second order with Am(IV)
* 2 Am(IV)Am(III) + Am(V)
* Am(IV) + Am(V)Am(III) +
Am(VI)
Am(VI) increases with
sulfate
Am(V)
3-8 M HClO4 and HCl
* 3 Am(V)
+4
H+Am(III)+2Am(VI)+2 H2O
Solution can impact oxidation state
stability
Redox kinetics
Am(III) oxidation by peroxydisulfate
Oxidation due to thermal
decomposition products
* SO4.-, HS2O8 Oxidation to Am(VI)
Acid above 0.3 M limits oxidation
* Decomposition of S2O82 Induction period followed by reduction
Rates dependent
upon temperature,
[HNO3], [S2O82-], and [Ag+2]
In carbonate proceeds through Am(V)
* Rate to Am(V) is proportional to
oxidant
* Am(V) to Am(VI)
Proportional to total Am
and oxidant
Inversely proportional to
K2CO3
15-6
Am solution chemistry: Redox kinetics
• Am(VI) reduction
H2O2 in perchlorate is 1st order for peroxide and Am
2 AmO22++H2O22 AmO2+ + 2 H++ O2
NpO2+
1st order with Am(VI) and Np(V)
* k=2.45E4 L / mol s
Oxalic acid reduces to equal molar Am(III) and Am(V)
• Am(V) reduction
Reduced to Am(III) in NaOH solutions
Slow reduction with dithionite (Na2S2O4), sulfite (SO32-),
or thiourea dioxide ((NH2)2CSO2)
Np(IV) and Np(V)
In both acidic and carbonate conditions
* For Np(IV) reaction products either Np(V) or Np(VI)
Depends upon initial relative concentration of
Am and Np
U(IV) examined in carbonate
15-7
Am solution chemistry
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Radiolysis
From alpha decay
1 mg 241Am release 7E14 eV/s
Reduction of higher valent Am related
to dose and electrolyte concentration
In nitric acid formation of HNO2
In perchlorate numerous species
produced
Cl2, ClO2, or ClComplexation chemistry
Primarily for Am(III)
F->H2PO4->SCN->NO3->Cl>ClO4
Hard acid reactions
Electrostatic interactions
* Inner sphere and outer
sphere
Outer sphere for
weaker ligands
Stabilities similar to trivalent
lanthanides
Some enhanced stability due to
participation of 5f electron in
bonding
15-8
Am solution
chemistry
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Hydrolysis
Mono-, di-, and trihydroxide
species
Am(V) appears to have 2 species,
mono- and dihydroxide
Am hydrolysis (from CHESS
database)
Am3++H2OAmOH2++H+:
log K =-6.402
Am+3++2H2OAm(OH)2++
2H : log K =-14.11
3++3H OAm(OH) +3
Am
3
+
H : log K2 =-25.72
Carbonate
Evaluated by spectroscopy
Includes mixed species
Am hydroxide carbonate
species
Based on solid phase analysis
Am(IV)
Pentacarbonate studied (log
b=39.3)
Am(V) solubility examined
1mM Am3+;
1 mM Am, 1 mM carbonate
15-9
Am solution chemistry: Organics
• Number of complexes examined
Mainly for Am(III)
• Generally stability of complex
increases with coordination sites
• With aminopolycarboxylic acids,
complexation constant increases
with ligand coordination
• Natural organic acid
Number of measurements
conducted
Measured by spectroscopy and
ion exchange
• TPEN (N,N,N’,N’-tetrakis(2pyridylmethyl)ethyleneamine)
0.1 M NaClO4, complexation
constant for Am 2 orders
greater than Sm
15-10
Am solvent extraction
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Tributylphosphate (TBP)
Am extracted from neutral or low acid solutions with high nitrate
Am(VI)
Oxidation with (NH4)10P2W17O61 to stabilize Am(VI)
100 % TBP from 1 M HNO3
* Separation factor 50 from Nd
Am separation from lanthanides
1 M ammonium thiocyanate aqueous phase
Dibutyl butylphosphonate (DBBP)
Phosphonate functional group
Similar to TBP, stronger extractant of Am
Trialkylphophine oxide (TRPO)
Increase in basicity of P=O functional group from TBP to DPPB to
TRPO
Am and Cm extraction from 1-2 M HNO3
30 % TRPO in kerosene
Am, Cm, tetravalent Np and Pu, hexavalent U extracted
* Actinides stripped with 5.5 M HNO3 (Am fraction)
TRPO with C6-C8 alkyl group
15-11
Am solvent extraction
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Bis(2-ethylhexyl)phosphoric acid (HDEHP)
Has been used to Am separation
Part of TALSPEAK
Extracts lanthanides stronger that actinides
TALSPEAK components
HDEHP
* Bis(2-ethyl-hexyl)phosphoric acid (HDEHP)
* HNO3
* DTPA
* Lactic acid
Carbamoylphosphine oxide (CMPO)
Synthesized by Horwitz
Based on DHDECMP extractions
* Recognized functional group, simplified ligand synthesis
* Purified by cation exchange
Part of TRUEX
TRUEX (fission products)
* 0.01 to 7 M HNO3
* 1.4 M TBP
* 0.2 M Diphenyl-N,N-dibutylcarbamoyl phosphine oxide (CMPO)
* 0.5 M Oxalic acid
* 1.5 M Lactic acid
* 0.05 M DTPA
15-12
CMPO
Am solvent extraction
• Tertiary amine salt
Low acid, high nitrate or chloride solution
(R3NH)2Am(NO3)5
• Quaternary ammonium salts (Aliquat 336)
Low acid, high salt solutions
Extraction sequence of Cm<Cf<Am<Es
Studies at ANL for process separation of Am
• Amide extractants
(R1,R2)N-C(O)-CR3H-C(O)-N(R1R2)
Diamide extractant
Basis of DIAMEX process
N,N’-dimethyl-N,N’-dibutyl-2-tetradecyl-malonamide
(DMDBTDMA)
DIAMEX with ligand in dodecane with 3-4 M HNO3
* Selective extraction over Nd
15-13
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Am/Ln solvent extraction
Extraction reaction
Am3++2(HA)2AmA3HA+3
H+
Release of protons upon
complexation requires
pH adjustment to achieve
extraction
* Maintain pH greater
than 3
Cyanex 301 stable in acid
HCl, H2SO4, HNO3
Below 2 M
Irradiation produces acids and
phosphorus compounds
Problematic extractions when
dosed 104 to 105 gray
New dithiophosphinic acid less
sensitive to acid concentration
R2PSSH; R=C6H5, ClC6H4,
FC6H4, CH3C6H4
Only synergistic
extractions with, TBP,
TOPO, or
tributylphosphine oxide
Aqueous phase 0.1-1 M
HNO3
Increased radiation
resistance
Distribution ratios of Am(III ) and Ln(III ) in 1.0 M
Cyanex 301‐heptane (16 mol% of Cyanex 301
neutralized before extraction contacts)
15-14
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Ion exchange separation Am
from
Cm
LiCl with ion exchange achieves separation from
lanthanide
Separation of tracer level Am and Cm has been
performed with displacement complexing
chromatography
DTPA and nitrilotriacetic acid in presence of
Cd and Zn as competing cations
displacement complexing chromatography
method is not suitable for large scale
Ion exchange has been used to separate trace levels of
Cm from Am
Am, Cm, and lanthanides sorbed to a cation
exchange resin at pH 2
Separation of Cm from Am was
performed with 0.01 % ethylenediaminetetramethylphosphonic acid at pH 3.4 in
0.1 M NaNO3
separation factor of 1.4
Separation of gram scale quantities of Am and Cm by
cation and anion exchange
use of a-hydroxylisobutyrate or
diethylenetriaminepentaacetic acid as an
eluting agent or a variation of eluant
composition by addition of methanol to nitric
acid
best separations were achieved under
high pressure conditions
* separation factors greater than 400
Distribution
coefficients of actinides and
lanthanides into Dowex 1 8 resin
15-15
from 10 M LiCl
Extraction chromatography
• Mobile liquid phase and stationary liquid phase
Apply results from solvent extraction
HDEHP, Aliquat 336, CMPO
* Basis for Eichrom resins
* Limited use for solutions with fluoride, oxalate, or
phosphate
DIPEX resin (Eichrom)
* Bis-2-ethylhexylmethanediphosphonic acid on inert support
* Lipophilic molecule
Extraction of 3+, 4+, and 6+ actinides
* Strongly binds metal ions
Need to remove organics from support
Variation of support
Silica for covalent bonding
Functional organics on coated ferromagnetic particles
* Magnetic separation after sorption
15-16
Am separation and purification
• Precipitation method
Formation of insoluble Am species
AmF3, K8Am2(SO4)7 , Am2(C2O4)3, K3AmO2(CO3)2
* Am(V) carbonate useful for separation from Cm
* Am from lanthanides by oxalate precipitation
Slow hydrolysis of dimethyloxalate
Oxalate precipitate enriched in Am
50 % lanthanide rejection, 4 % Am
Oxidation of Am(VI) by K2S2O8 and precipitation of Cm(III)
• Pyrochemical process
Am from Pu
O2 in molten salt, PuO2 forms and precipitates
Partitioning of Am between liquid Bi or Al and molten
salts
* Kd of 2 for Al system
Separation of Am from PuF4 in salt by addition of OF2
* Formation of PuF6, volatility separation
15-17
CHEM 312: Lecture 15 Americium and Curium
Chemistry
• Readings: Am and Cm
chemistry chapters
Link on web page
• Combined due to similar
chemical properties of elements
Cover Am then Cm
• Nuclear properties
• Production of isotopes
• Separation and purification
• Metallic state
• Compounds
• Solution chemistry
• Coordination chemistry
15-18
CHEM 312: Lecture 15 Americium and Curium
Chemistry Part 2
• Readings: Am and Cm
chemistry chapters
Link on web page
• Combined due to similar
chemical properties of elements
Cover Am then Cm
• Nuclear properties
• Production of isotopes
• Separation and purification
• Metallic state
• Compounds
• Solution chemistry
• Coordination chemistry
15-19
Am metal and alloys
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Preparation of Am metal
Reduction of AmF3 with Ba or Li
Reduction of AmO2 with La
Bomb reduction of AmF3 with Ca
Decomposition of Pt5Am
1550 °C at 10-6 torr
La or Th reduction of AmO2 with
distillation of Am
Metal properties
Ductile, non-magnetic
Double hexagonal closed packed
(dhcp) and fcc
Evidence of three phase between room
temperature and melting point at 1170
°C
Alpha phase up to 658 °C
Beta phase from 793 °C to 1004
°C
Gamma above 1050 °C
Some debate in literature
Evidence of dhcp to fcc at 771 °C
Interests in metal properties due to 5f
electron behavior
Delocalization under pressure
Different crystal structures
* Conversion of dhcp to fcc
Discrepancies between different
experiments and theory
Alloys investigated with 23 different elements
Phase diagrams available for Np, Pu,
and U alloys
15-20
Am compounds: Oxides and Hydroxides
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AmO, Am2O3, AmO2
Non-stoichiometric phases between
Am2O3 and AmO2
AmO lattice parameters varied in experiments
4.95 Å and 5.045 Å
Difficulty in stabilizing divalent Am
Am2O3
Prepared in H2 at 600 °C
Oxidizes in air
Phase transitions with temperature
bcc to monoclinic between 460 °C
and 650 °C
Monoclinic to hexagonal between
800 °C and 900 °C
AmO2
Heating Am hydroxides, carbonates,
oxalates, or nitrates in air or O2 from 600
°C to 800 °C
fcc lattice
Expands due to radiation damage
Higher oxidation states can be stabilized
Cs2AmO4 and Ba3AmO6
Am hydroxide
Isostructural with Nd hydroxides
Crystalline Am(OH)3 can be formed, but
becomes amorphous due to radiation
damage
Complete
degradation in 5 months
for 241Am hydroxide
Am(OH)3+3H+,Am3++3H2O
logK=15.2 for crystalline
Log K=17.0 for amorphous
15-21
Am organic compounds
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From precipitation (oxalates) or solution evaporation
Includes non-aqueous chemistry
AmI3 with K2C8H8 in THF
Yields KAm(C8H8)2
Am halides with molten Be(C5H5) forms Am(C5H5)3
Purified by fractional sublimation
Characterized by IR and absorption spectra
15-22
Am coordination chemistry
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Little known about Am coordination chemistry
46 compounds examined
XRD and compared to isostructural lanthanide compounds
Structural differences due to presence of oxo groups in oxidized Am
Halides
Coordination numbers 7-9, 11
Coordination include water
AmCl2(H2O)6+
* Outer sphere Cl may be present
15-23
Am coordination chemistry
• Oxides
Isostructural with Pu oxides
AmO may not be correct
Am(V)=O bond distance of 1.935 Å
Am2O3 has distorted Oh symmetry with Am-O
bond distances of 2.774 Å, 2.678 Å, and 1.984
15-24
Am coordination chemistry
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Cyclopentadienyl (CP) ligands
Am(C5H5)3
Isostructural with Pu(III) species
* Not pyrophoric
Absorbance on films examined
* Evaluated 2.8 % relative bond covalency
* Indicates highly ionic bonding for species
* Data used for calculations and discussion of 5f and 6d
orbitals in interactions
Bis-cyclooctatetraenyl Am(III) KAm(C8H8)2
In THF with 2 coordinating solvent ligands
Decomposes in water, burns in air
XRD shows compound to be isostructural with Pu and Np
compounds
From laser ablation mass spectra studies, examination of
molecular products
Differences observed when compared to Pu and Np
compounds
Am 5f electrons too inert to form sigma bonds with
organic, do not participate
15-25
Curium: Nuclear properties
• Isotopes from mass 237 to
251
• 242Cm, t1/2=163 d
122 W/g
Grams of oxide glows
Low flux of 241Am
target decrease fission
of 242Am, increase yield
of 242Cm
• 244Cm, t1/2=18.1 a
2.8 W/g
• 248Cm, t1/2= 3.48E5 a
8.39% SF yield
Limits quantities to 1020 mg
Target for production
of transactinide
elements
15-26
Cm Production
• From successive neutron capture of higher Pu isotopes
242Pu+n243Pu (b-, 4.95 h)243Am+n244Am (b-, 10.1 h)244Cm
Favors production of 244,246,248Cm
Isotopes above 244Cm to 247Cm are not isotopically pure
Pure 248Cm available from alpha decay of 252Cf
• Large campaign to product Cm from kilos of Pu
• 244Cm separation
Dissolve target in HNO3 and remove Pu by solvent extraction
Am/Cm chlorides extracted with tertiary amines from 11 M LiCl
in weak acid
Back extracted into 7 M HCl
Am oxidation and precipitation of Am(V) carbonate
• Other methods for Cm purification included NaOH, HDEHP, and
EDTA
Discussed for Am
15-27
Cm aqueous chemistry
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Trivalent Cm
242Cm at 1g/L will boil
9 coordinating H2O from fluorescence
Decreases above 5 M HCl
7 waters at 11 M HCl
In HNO3 steady decrease from 0 to 13 M
5 waters at 13 M
Stronger complexation with NO3Inorganic complexes similar to data for Am
Many constants determined by TRLFS
Hydrolysis constants (Cm3++H2OCmOH2++H+)
K11=1.2E-6
Evaluated under different ionic strength
15-28
Cm atomic and spectroscopic data
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Cm(III) absorbance
Weak absorption in near-violet
region
Solution absorbance shifted 20-30 Å
compared to solid
Reduction of intensity in solid
due to high symmetry
* f-f transitions are symmetry
forbidden
Spin-orbit coupling acts to reduce
transition energies when compared
to lanthanides
Cm(IV) absorbance
Prepared from dissolution of CmF4
CmF3 under strong fluorination
conditions
5f7 has enhanced stability
Half filled orbital
Large oxidation potential for
IIIIV
Cm(IV) is metastable
15-29
Absorption and fluorescence process of Cm3+
Optical Spectra
Fluorescence Process
30
Wavenumber (10
3
-1
cm )
H
G
F
Emissionless
Relaxation
20
A
7/2
Excitation
10
Fluorescence
Emission
15-30
0
Z
7/2
Cm fluorescence
• Fluoresce from 595-613
nm
Attributed to
6D 8S
7/2
7/2
transition
Energy dependent
upon coordination
environment
Speciation
Hydration
complexation
constants
15-31
Cm separation and purification:
Similar to Am
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Solvent extraction
Organic phosphates
Function of ligand structure
* Mixed with 6 to 8 carbon chain better than TBP
HDEHP
From HNO3 and LiCl
CMPO
Oxidation state based removal with different stripping agent
Extraction of Cm from carbonate and hydroxide solutions, need to keep
metal ions in solution
Organics with quaternary ammonium bases, primary amines,
alkylpyrocatechols, b-diketones, phenols
Ion exchange
Anion exchange with HCl, LiCl, and HNO3
Includes aqueous/alcohol mixtures
Formation of CmCl4- at 14 M LiCl
* From fluorescence spectroscopy
Precipitation
Separation from higher valent Am
10 g/L solution in base
Precipitation of K5AmO2(CO3)3 at 85 °C
Precipitation of Cm with hydroxide, oxalate, or fluoride
15-32
Cm metallic state
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Preparation of Cm metal
CmF3 reduction with Ba or Li
Dry, O2 free, and above 1600 K
Reduction of CmO2 with Mg-Zn alloy
in MgF2/MgCl2
Melting point 1345 °C
Higher than lighter actinides Np-Am
Similar to Gd (1312 °C)
Two states
Double hexagonal close-packed (dhcp)
Neutron diffraction down to 5 K
No structure change
fcc at higher temperature
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XRD studies on 248Cm
Magnetic susceptibility studies
Antiferrimagnetic transition near 65 K
200 K for fcc phase
Metal susceptible to corrosion due to self heating
Formation of oxide on surface
Alloys
Cm-Pu phase diagram studied
Noble metal compounds
CmO2 and H2 heated to 1500 K in
Pt, Ir, or Rh
* Pt5Cm, Pt2Cm, Ir2Cm, Pd3Cm,
Rh3Cm
15-33
Cm oxide compounds
• Cm2O3
Thermal decomposition of CmO2 at 600 °C and 10-4 torr
Mn2O3 type cubic lattice
Transforms to hexagonal structure due to radiation
damage
Monoclinic at 800 °C
• CmO2
Heating in air, thermal treatment of Cm loaded resin, heating
Cm2O3 at 600 °C under O2, heating of Cm oxalate
Shown to form in O2 as low as 400 °C
Evidence of CmO1.95 at lower temperature
fcc structure
Magnetic data indicates paramagnetic moment attributed to
Cm(III)
Need to re-evaluate electronic ground state in oxides
• Oxides
Similar to oxides of Pu, Pr, and Tb
Basis of phase diagram
BaCmO3 and Cm2CuO4
Based on high T superconductors
15-34
Cm compounds do not conduct
Cm compounds
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Cm(OH)3
From aqueous solution, crystallized by aging in water
Same structure as La(OH)3; hexagonal
Cm2(C2O4)3.10H2O
From aqueous solution
Stepwise dehydration when heated under He
Anhydrous at 280 °C
Converts to carbonate above 360 °C
* TGA analysis showed release of water (starting at 145 °C)
Converts to Cm2O3 around 500 °C
Cm(NO3)3
Evaporation of Cm in nitric acid
From TGA, decomposition same under O2 and He
Dehydration up 180 °C, melting at 400 °C
Final product CmO2
Oxidation of Cm during decomposition
Organometallics
Studies hampered by radiolytic properties of Cm
Some compounds similar to Am
Cm(C5H5)3 form CmCl3 and Be(C5H5)2
Weak covalency of compound
Strong fluorescence
15-35
Review
• Production and purification of Am and Cm isotopes
Suitable reactions
Basis of separations from other actinides
• Formation of Am and Cm metallic state and properties
Number of phases, melting points
• Compounds
Range of compounds, limitations on data
• Solution chemistry
Oxidation states
• Coordination chemistry
Organic chemistry reactions
15-36
Questions
• What is the longest lived isotope of Am?
• Which Am isotope has the highest neutron induced
fission cross section?
• What are 3 ligands used in the separation of Am?
What are the solution conditions?
• What column methods are useful for separating Am
from the lanthanides?
• Which compounds can be made by elemental reactions
with Am?
• What Am coordination compounds have been
produced?
• What is the absorbance spectra of Am for the different
oxidation states?
• How can Am be detected?
15-37
Questions
• Which Cm isotopes are available for chemical
studies?
• Describe the fluorescence process for Cm
What is a good excitation wavelength?
• What methods can be use to separate Cm from
Am?
• How many states does Cm metal have? What
is its melting point?
• What are the binary oxides of Cm? Which will
form upon heating in normal atmosphere?
15-38
Questions
• Comment on blog
• Provide response to PDF Quiz 15
15-39