Radiochemistry Fuel Cycle Summer School

Lecture 1: Introduction

Class organization
 3utcomes
 Grading

aistory

Chart of the nuclides
 escription and use of chart
 ata

Radiochemistry introduction
 ½tomic properties
 Nuclear nomenclature
 X-rays
 Types of decays
 forces

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 Introduction

Coursed developed with support from
epartment of Energy-Nuclear
Energy

Extension of education and research
efforts in the UNLV Radiochemistry
program

Course designed to increase potential
pool of researchers for the nuclear
fuel cycle
 Nuclear fuel
 Separations
 Waste forms
 Safeguards
 Nuclear reactors

Course will emphasize the role of
radiochemistry in the nuclear fuel
cycle

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 Course overview

Intensive course in radiochemistry with a focus on the nuclear fuel
cycle

Radiochemistry includes physics of radioactive decay and
chemistry of radioisotopes
 Intellectual intersection of the periodic table and chart of the
nuclides

Course topics
 Chart of the nuclides
 etails on alpha decay, beta decay, gamma decay, and fission
 Methods and data from the investigation of nuclear
properties
 Fundamental chemical properties in radiation and
radiochemistry
 Radioisotope production and
 Radiochemistry in research and technology

Textbooks and published literature are used a reading material

1st course: Input from students valued

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 Course overview

Course has lecture and laboratory component
 Lectures daily
0900-1200
TBE Room B178
 Laboratory varied
Set laboratories to provided background
å Radiation safety
å ½lpha spectroscopy
å Gamma spectroscopy
å Uranium/plutonium separations
å Zr32-U32 synthesis
Research on an aspect of the nuclear fuel cycle
å ½ssist in ongoing research projects

http://radchem.nevada.edu/classes/rfss/index.html

Webpage is developed as resource for students
 Lectures, readings, tests, homework, links
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 3utcomes
1. Understand, utilize, and apply the chart of
the nuclides to radiochemistry and nuclear
technology
 Bring chart of nuclide to class
 Understand chart of the nuclide
structure
 ½ccess and utilize presented data
2. Understand the fundamentals of nuclear
structure
 Why do nuclei have shapes other than
spherical
 Relationship between shape and
behavior
3. Understand chemical properties of
radioelements
 Focus on actinides
Filling of 5f electron orbitals
 Technetium, promethium
Radioelements Z<83 |
 3utcomes
4. Comprehend and evaluate nuclear reactions and
the production of isotopes
 Use chart of the nuclides
Cross section data
 Reaction particles
Neutrons, alpha, ions, photons
 Reaction energies
Mass differences
5. Comprehend types and descriptions of
radioactive decay
 Expected decay based on location of isotope
in chart of the nuclides
 ecay modes relationship with half-life
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 3utcomes
6. Utilization of radiochemistry in research
 Evaluation of concentration
 Behavior of radioelements
 Exploitation of isotopes
7. Investigate modern topics relating
radiochemistry to the nuclear fuel cycle
 Research basis in laboratory
 Literature review
 Presentation of results
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 Grading: Lecture course

Pop-quizzes at end of lecture (25 %)
 Based upon presented information

Five comprehensive quizzes (15 % each)
 Based on topic covered in lecture and pop
quizzes

Goal of quizzes is material comprehension

Nature of comprehensive quizzes
 In class
 Take home

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 Grading: Laboratory

4 groups for initial
laboratories

Write up for 4 laboratories
(10 % each)
 Gamma spectroscopy
 ½lpha Spectroscopy
 Zr32-Pu32 synthesis
 U-Pu separation
3ne report from
each group

Report on research (30 %)

Presentation of research (30
%)
 15 minute presentation
at end of course |
 Laboratory Modules

Radiation safety
 1st module taken by all students
Swipes, handing of material, general
protocols

½lpha spectroscopy
 Inverse square law
 Isotopics
 ecay energy branching

Gamma spectroscopy
 Calibration
 Measuring samples
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 Laboratory Modules

Radiochemical separations
 Solvent extraction with tributylphosphate
 Separation of Pu from U

Formation of oxide ceramics
 Precipitation from salts
 Zr32
 Zr32±U32
 Basis for formation of nuclear fuel

Focus on concepts useful for the nuclear fuel

cycle
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 Grading: Laboratory

Reports format from manuscript preparation
 ½bstract
 Introduction
Background
Why is the research performed
 Experimental
Methods
Equipment
 Results and discussion
What was observed, what does it mean
 Conclusion
Restatement of main discussion points
½nswers question posed in introduction
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 3utline: Lectures
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 aistory of Radiation Research

1896 iscovery of radioactivity
 Becquerel used K2U32(S34)2‡ a23 exposed
to sunlight and placed on photographic
plates wrapped in black paper
 Plates revealed an image of the uranium
crystals when developed

1898 Isolation of radium and polonium
 Marie and Pierre Curie isolated from U ore

1899 Radiation into alpha, beta, and gamma
components, based on penetration of objects and
ability to cause ionization
 Ernest Rutherford identified alpha

1909 ½lpha particle shown to be ae nucleus
 Charge to mass determined by Rutherford

1911 Nuclear atom model
 Plum pudding by Rutherford

1912 evelopment of cloud chamber by Wilson

1913 Planetary atomic model (Bohr Model)

1914 Nuclear charge determined from X rays
 etermined by Moseley in Rutherford¶s
laboratory | |
 aistory

1919 ½rtificial transmutation by
nuclear reactions
 Rutherford bombarded 14N with
alpha particle to make 173

1919 evelopment of mass
spectrometer

1928 Theory of alpha radioactivity
 Tunneling description by Gamow

1930 Neutrino hypothesis
 Fermi, mass less particle with ½
spin, explains beta decay

1932 First cyclotron
 Lawrence at UC Berkeley
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 aistory

1932 iscovery of neutron
 Chadwick used scattering data

to calculate mass, Rutherford
knew ½ was about twice Z.   
|  €
€p |

 

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Lead to proton-neutron nuclear
model 
F

1934 iscovery of artificial | €€p| 

radioactivity
 mean Frédéric moliot & Irène
Curie showed alphas on ½l
formed P

1938 iscovery of nuclear fission
 From reaction of U with
neutrons, aahn and Meitner

1942 First controlled fission reactor

1945 First fission bomb tested

1947 evelopment of radiocarbon
dating
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Radioelements

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 Technetium

Confirmed in a ecember 1936
experiment at the University of Palermo
 Carlo Perrier and Emilio Segrè.
 Lawrence mailed molybdenum foil
that had been part of the deflector
in the cyclotron
 Succeeded in isolating
the isotopes 95,97Tc
 Named after
Greek word IJİȤȞȘIJȩȢ, meaning
artificial
University of Palermo officials
wanted them to name their
discovery "¦
", after
the Latin name
for Palermo, 

 Segre and Seaborg isolate 99mTc
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 Promethium

Promethium was first produced and
characterized at 3RNL in 1945 by macob ½.
Marinsky, Lawrence E. Glendenin and Charles
. Coryell

Separation and analysis of the fission products
of uranium fuel irradiated in the Graphite
Reactor

½nnounced discovery in 1947

In 1963, ion-exchange methods were used at
3RNL to prepare about 10 grams of Pm from
used nuclear fuel
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 Np synthesis

Neptunium was the first synthetic transuranium element of the
actinide series discovered
 isotope 239Np was produced by McMillan and ½belson in
1940 at Berkeley, California
 bombarding uranium with cyclotron-produced neutrons
238U(n,)239U, beta decay of 239U to 239Np (t =2.36 days)
1/2
 Chemical properties unclear at time of discovery
½ctinide elements not in current location
In group with W

Chemical studies showed similar properties to U

First evidence of 5f shell

Macroscopic amounts
 237Np
238U(n,2n)237U

å Beta decay of 237U

10 microgram
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 Pu synthesis

Plutonium was the second transuranium element of the actinide
series to be discovered
 The isotope 238Pu was produced in 1940 by Seaborg,
McMillan, Kennedy, and Wahl
 deuteron bombardment of U in the 60-inch cyclotron at
Berkeley, California
238U(2a, 2n)238Np

å Beta decay of 238Np to 238Pu

 3xidation of produced Pu showed chemically different

239Pu produced in 1941
 Uranyl nitrate in paraffin block behind Be target bombarded
with deuterium
 Separation with fluorides and extraction with diethylether
 Eventually showed isotope undergoes slow neutron fission

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 ½m and Cm discovery

Problems with identification due to chemical
differences with lower actinides
 Trivalent oxidation state

239Pu(4ae,n)242Cm
 Chemical separation from Pu
 Identification of 238Pu daughter from alpha
decay

½m from 239Pu in reactor
 ½lso formed 242Cm

ifficulties in separating ½m from Cm and
from lanthanide fission products
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 Bk and Cf discovery

Required ½m and Cm as targets
 Needed to produce theses isotopes in sufficient
quantities
Milligrams
 ½m from neutron reaction with Pu
 Cm from neutron reaction with ½m

241½m(4ae,2n)243Bk
 Cation exchange separation

242Cm(4ae,n)245Cf
 ½nion exchange

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Cf data

owex 50 resin
at 87 °C, elute
with ammonium
citrate

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 Einsteinium and Fermium

ebris from Mike test
 1st thermonuclear test

New isotopes of Pu
 244 and 246
Successive neutron capture of 238U
 Correlation of log yield versus atomic mass

Evidence for production of transcalifornium isotopes
 aeavy U isotopes followed by beta decay

Ion exchange used to demonstrate new isotopes

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 Md, No, and Lr discovery

1st atom-at-a-time chemistry
 253Es(4a,n)256Md

Required high degree of chemical separation

Use catcher foil
 Recoil of product onto foil
 issolved ½u foil, then ion exchange

No controversy
 Expected to have trivalent chemistry
 1st attempt could not be reproduced
Showed divalent oxidation state
 246Cm(12C,4n)254No
½lpha decay from 254No
Identification of 250Fm daughter using ion exchange

For Lr 249, 250, 251Cf bombarded with 10,11B

New isotope with 8.6 MeV, 6 second half life
 Identified at 258Lr
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 Types of ecay
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 Fission Products

Fission yield curve varies with fissile isotope

2 peak areas for U and Pu thermal neutron induced fission

Variation in light fragment peak
7  

Influence of neutron energy observed

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 Chart of the Nuclides

Presentation of data on nuclides
 Information on chemical element
 Nuclide information
Spin and parity (0+ for even-even nuclides)
Fission yield
 Stable isotope
Isotopic abundance
Reaction cross sections
Mass

Radioactive isotope
 aalf-life
 Modes of decay and energies
 Beta disintegration energies
 Isomeric states
 Natural decay series
 Reaction cross sections
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 Chart of Nuclides

ecay modes
 ½lpha
 Beta
 Positron
 Photon
 Electron capture
 Isomeric transition
 Internal conversion
 Spontaneous fission
 Cluster decay

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 Chart of the Nuclides Questions

aow many stable isotopes of Ni?

What is the mass and isotopic abundance of 84Sr?

Spin and parity of 201ag?

ecay modes and decay energies of 212Bi

What are the isotopes in the 235U decay series?

What is the half-life of 176Lu?

What is the half-life of 176Yb

aow is 238Pu produced?

aow is 239Pu made from 238U

Which actinide isotopes are likely to undergo
neutron induced fission?

Which isotopes are likely to undergo alpha decay?

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 Radiochemistry Introduction

Radiochemistry
 Chemistry of the radioactive isotopes and elements
 Utilization of nuclear properties in evaluating and understanding chemistry
 Intersection of chart of the nuclides and periodic table

½tom
 Z and N in nucleus (10-14 m)
 Electron interaction with nucleus basis of chemical properties (10-10 m)
Electrons can be excited
å aigher energy orbitals
å Ionization
R Binding energy of electron effects ionization
 Isotopes
Same Z different N
 Isobar
Same ½ (sum of Z and N)
 Isotone
Same N, different Z
 Isomer
Nuclide in excited state
99mTc
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 Terms and decay modes: Utilization of
chart of the nuclides

Identify the isomer, isobars, isotones, and isotopes
 60mCo, 57Co, 97Nb, 58Co, 57Ni, 57Fe, 59Ni, 99mTc

Identify the daughter from the decay of the following
isotopes
 210Po
 196Pb
 204Bi
 209Pb
 222½t
 212Bi
 208Pb

aow is 14C naturally produced

Identify 5 naturally occurring radionuclides with Z<84
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 X-rays

Electron from a lower level is removed
 electrons of the higher levels can come to occupy
resulting vacancy
 energy is returned to the external medium as
electromagnetic radiation

radiation called an X-ray
 discovered by Roentgen in 1895
 In studying x-rays radiation emitted by uranium
ores Becquerel et. al. (P. and M. Curie) discovered
radioactivity in 1896

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 X-rays

Removal of K shell electrons
2 2 3
 Electrons coming from the 22
higher levels will emit photons 2

2222222222222222222222222222 22222
while falling to this K shell 2 
series of rays (frequency R 222222222222222
2222
2
or wavelength P) are 
22222222222

2
noted as K^, K , K 2 
If the removed electrons
are from the L shell, 2
noted as L^, L , L

In 1913 Moseley studied these
frequencies R, showing that:

R  !  › %

where Z is the atomic number and, ½
and Z0 are constants depending on
the observed transition.

K series, Z0 = 1, L series, Z0 = 7.4.

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 Fundamentals of x-rays

X-rays
 X-ray wavelengths from 1E-5 angstrom to
100 angstrom
e-acceleration of high energy electrons
Electron transitions from inner orbitals
å Bombardment of metal with high
energy electrons
å Secondary x-ray fluorescence by
primary x-rays
å Radioactive sources
å Synchrotron sources
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 aalf Lives

N/No=e-Pt
N=Noe- Pt
P=(ln 2)/t1/2
P is decay constant

5||   '? | 

 Equation questions

Calculate decay constant for the following
 75Se
 74mGa
 81Zn

What percentage of 66½s remains from a given
amount after 0.5 seconds

aow long would it take to decay 90 % of 65Zn?

If you have 1 g of 72Se initially, how much
remains in 12 days?

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 Forces in nature

Four fundamental forces in nature
 ½ll interactions in the universe are the result of these forces

Gravity
 Weakest force
 most significant when the interacting objects are massive,
such as planets, stars, etc.

Weak interaction
 Beta decay

Electromagnetic force
 Most observable interactions

Strong interaction
 Nuclear properties

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Fundamental Forces

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Classic and relativistic

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 Use of relativistic terms

relativistic expressions

photons, neutrinos

Electrons > 50 keV

nucleons when the
kinetic energy/nucleon
exceeds 100 MeV

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 Wavelengths and energy

Planck evaluated minimum from ËExËt when he studied the
radiation emitted by a black body at a given temperature

Quantum called Planck¶s constant h (h = 6.6 10-34 m.s).
 radiation conveys energy E in the form of quanta E = hR
R the frequency of the emitted radiation

Based on the wave mechanics worked out by de Broglie
[ P = h/p
 P is the wavelength associated with any moving particle with
the momentum p
m@ (

m


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 Wavelengths

Photon relationships

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 Particle Physics: Boundary of Course

fundamental particles of nature and interaction
symmetries

Particles classified as fermions or bosons
 Fermions obey the Pauli principle
antisymmetric wave functions
half-integer spins
å Neutrons, protons and electrons
Bosons do not obey Pauli principle
å symmetric wave functions and integer spins
R Photons

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 Particle physics

Particle groups divided
 leptons (electron)
 hadrons (neutron and
proton)
hadrons can
interact via the
strong interaction
Both can interact
with other forces
Fermionic aadrons
comprised of
quarks

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 Topic review

aistory of nuclear physics research

iscovery of the radioelements
 Methods and techniques used

Types of radioactive decay

Understand and utilize the data presented in the
chart of the nuclides

Utilize the fundamental decay equations

Identify common fission products

efine X-rays

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 Study Questions

What are the course outcomes?

What were important historical moments in
radiochemistry?

Who were the important scientists in the
investigation of nuclear properties?

What are the different types of radioactive
decay?

What are some commonalities in the discovery
of the actinides?

Provide 5 radioelements
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 Pop Quiz

Provide 10 facts about 129I

Fill in the periodic table

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