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CHEM 312 Lecture 9: Nuclear Reactions. Readings: Modern Nuclear Chemistry, Chapter 10; Nuclear and Radiochemistry, Chapter 4 Notation Energetics of Nuclear Reactions Reaction Types and Mechanisms Barriers Scattering Nuclear Reaction Cross Sections Reaction Observables Scattering

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chem 312 lecture 9 nuclear reactions
CHEM 312 Lecture 9: Nuclear Reactions

Readings: Modern Nuclear Chemistry, Chapter 10; Nuclear and Radiochemistry, Chapter 4


Energetics of Nuclear Reactions

Reaction Types and Mechanisms



Nuclear Reaction Cross Sections

Reaction Observables


Direct Reactions

Compound Nuclear Reactions

Photonuclear Reactions


nuclear reactions
Nuclear Reactions
  • Nucleus reactions with a range of particles
    • nucleus, subatomic particle, or photon to produce other nuclei
    • Short time frame (picosecond)
  • First nuclear reaction from Rutherford
    • What reaction was this?
  • Number of terms conserved during nuclear reactions
    • Number of nucleons
      • except in reactions involving creation or annihilation of antinucleons
    • charge
    • Energy
    • momentum
    • angular momentum
    • parity
  • Q is the energy of the reaction
    • positive Q corresponds to energy release
    • negative Q to energy absorption
  • Q terms given per nucleus transformed

Q=-1.193 MeV

  • Reaction Q values
    • Not necessarily equal to kinetic energy of bombarding particles for the reaction to occur
      • Need more energy than Q value for reaction to occur
        • Reaction products will have kinetic energy that needs to come from reaction
  • Conservation of momentum
    • Some particles’ kinetic energy must be retained by products as kinetic energy
  • Amount retained as kinetic energy of products
    • Based on projectile mass
    • Retained kinetic energy becomes smaller with increasing target mass
      • Equation for kinetic energy (T):
  • What does this mean about reaction
    • Heavier target or heavier projectile?
      • 248Cm + 18O266Rf

248Cm Projectile

18O Projectile

energetics reaction barrier
Energetics: Reaction Barrier
  • Need to consider comparison of laboratory and center of mass frame
    • Laboratory frame
      • conservation of momentum considers angle of particles
    • Center of mass
      • Total particle angular momentum is zero
  • Kinetic energy carried by projectile (Tlab) is not fully available for reaction
    • Tlab - Tcm = T0
  • For reaction to occur Q + T0 must be achieved
    • Basis for threshold reaction
    • Q + T0 > 0
reaction barrier
Reaction Barrier
  • Threshold energy (minimum energy for reaction)
  • Fraction of bombarding particle’s kinetic energy retained as kinetic energy of products becomes smaller with increasing mass of target
    • Heavier target or heavier projectile?
    • 248Cm + 18O266Rf

Solve of laboratory T

A for mass

reaction barrier threshold energy
Reaction Barrier: Threshold Energy
  • Consider the 14N(a,p)17O reaction
    • Find threshold energy
      • Q from mass excess
        • Q=2.425 + 2.863 – 7.289 – (-0.809) = -1.19 MeV
  • Reaction barrier also induced by Coulomb interaction
    • Need to have enough energy to react and overcome Coulomb barrier
      • From charge repulse as particle approach each other
        • R is radius
        • ro =1.1 to 1.6 fm
  • Equation can vary due to ro
  • Vc can be above threshold energy
  • Center of mass, need to bring to laboratory frame
    • Consider kinetic energy carried by projectile
    • 3.36x ((14+4)/14) = 4.32 MeV alpha needed for reaction
cross section limits
Cross Section Limits
  • Reaction cross section of R2 is approximated at high energies
    • Wave nature of incident particle causes upper limit of reaction cross section to include de Broglie wavelength
      • So cross section can be larger that area
  • Collision between neutron and target nucleus characterized by distance of closest approach
    • B is impact parameter
cross section
Cross section

sl is partial cross section of given angular momentum l

  • Quantum-mechanical treatment Tl is the transmission coefficient for reaction of a neutron with angular momentum l
    • Represents fraction of incident particles with angular momentum l that penetrate within range of nuclear forces
      • Provides summing term to increase cross section
      • Reason why cross section can be larger than physical size of nucleus
  • General trends for neutron and charged particles
    • Charged particle cross section minimal at low energy
    • Neutron capture cross section maximum at low energy
types of experiments excitation functions
Types of Experiments: Excitation Functions
  • variation of reaction cross section with incident energy
  • shape can be determined by exposing several target foils in same beam with energy-degrading
  • provide information about probabilities for emission of various kinds of particles and combinations of particles in nuclear reactions
    • formation of given product implies what particles were ejected from the target nuclide
  • Range of cross sections can be evaluated
low energy reactions with light projectiles
Low-Energy Reactions with Light Projectiles
  • Elastic scattering
    • kinetic energy conserved
  • Slow-Neutron Reactions
    • Purest example of compound-nucleus behavior
      • 1/v law governs most neutron cross sections in region of thermal energies
    • neutrons available only from nuclear reactions
      • Range of energies can be obtained
  • Deuteron Reactions
    • Prevalence of one nucleon stripping
      • large size and loose binding of deuteron
      • Only proton and neutron in deuteron nucleus
        • Proton charge carries both nucleons
high energy reactions
High Energy Reactions
  • Spallation Products
    • products in immediate neighborhood of target element found in highest yields
      • within 10 to 20 mass numbers
    • yields tend to form in two regions
    •  stability for medium-weight products
    • neutron-deficient side of stability with increasing Z of products
    • Used to produce beam of neutrons at spallation neutron source
      • Heavy Z will produce 20-30 neutrons
      • Basis of Spallation neutron source (
  • High-Energy Fission
    • single broad peak in mass-yield curve instead of double hump seen in thermal-neutron fission
    • many neutron-deficient nuclides
      • especially among heavy products
      • originate from processes involving higher deposition energies
      • lower kinetic energies
      • do not appear to have partners of comparable mass
      • arise from spallation-like or fragmentation reactions
high energy reactions1
High-Energy Reactions
  • Mass-Yield Curves
    • at low energies, compound-nucleus picture dominates
      • as energy increases importance of direct reactions and preequilibrium(pre-compound nucleus) emission increase
      • above 100 MeV, nuclear reactions proceed nearly completely by direct interactions
    • products down to mass number 150 are spallation products
    • those between mass numbers 60 and 140 are fission products
  • Cascade-Evaporation Model
    • Above 100 MeV reactions
    • energy of the incident proton larger than interaction energy between the nucleons in the nucleus
    • Wavelength less than average distance between nucleons
      • proton will collide with one nucleon at a time within the nucleus
        • high-energy proton makes only a few collisions in nucleus
        • Produces nucleons with high energy
heavy ion reactions
Heavy Ion Reactions
  • Inelastic scattering
    • scattering in which some of projectile’s kinetic energy transformed into excitation of target nucleus
      • greatest importance at large impact parameters
    • heavy ions valuable
      • can excite high-spin states in target nuclei because of large angular momenta
  • Can experience Coulomb excitation
    • high charges
    • below Coulomb barrier heights and excite nuclei by purely electromagnetic interactions
  • Transfer Reactions
    • stripping and pickup reactions prevalent with heavy ions
      • take place at impact parameters just below those at which interactions are purely Coulombic
    • angular distributions show oscillatory, diffraction-like pattern when transfer reaction to single, well-defined state observed
heavy ion reactions deep inelastic reactions
Heavy Ion Reactions: Deep Inelastic Reactions
  • Relatively large amounts of nuclear matter transferred between target and projectile
    • Show strongly forward-peaked angular distributions
    • “Grazing contact mechanism”
  • Products with masses in vicinity of projectile mass appear at angles other than classical grazing angle
    • Relatively small kinetic energies
  • Total kinetic energies of products strongly correlated with amount of mass transfer
    • Increasing mass difference of product and projectile lowers kinetic energy
  • Product will dissociate into two fragments
    • Appreciable fraction of incident kinetic energy dissipated and goes into internal excitation
compound nucleus reactions
Compound-Nucleus Reactions
  • compound-nucleus formation can only take place over a restricted range of small impact parameters
    • can define critical angular momentum above which complete fusion cannot occur
    • cf/R decreases with increasing bombarding energy
  • Neutron deficient heavy ions produce compound nuclei on neutron-deficient side of  stability belt
  • Heavy ion of energy above Coulomb barrier brings enough excitation energy to evaporate several nucleons
    • 5-10 MeV deexcitation for neutron evaporation
  • heavy-ion reactions needed for reaching predicted island of stability around Z=114 to Z=184
  • U is excitation energy, MAand Ma masses of target and projectile, Ta is projectile kinetic energy, Sa is projectile binding energy in compound nucleus
photonuclear reactions
Photonuclear reactions
  • Reactions between nuclei and low- and medium-energy photons dominated by giant resonance
    • Excitation function for photon absorption goes through a broad maximum a few MeV wide
      • Due to excitation of dipole vibrations of protons against neutrons in the nucleus
  • Resonance peak varies smoothly with A
    • 24 MeV at 16O
    • 13 MeV at 209Bi
  • Peak cross sections are 100-300 mb
  • (, p), (, n), (,a) reactions

origin of elements
Origin of Elements
  • Gravitational coalescence of H and He into clouds
  • Increase in temperature to fusion
  • Proton reaction
    • 1H + n → 2H + g
    • 2H + 1H → 3He
    • 2H + n → 3H
    • 3H + 1H → 4He + g
    • 3He + n → 4He + g
    • 3H + 2H → 4He + n
    • 2H + 2H → 4He + g
    • 4He + 3H → 7Li + g
    • 3He+4He → 7Be+ g
      • 7Be short lived
      • Initial nucleosynthesis lasted 30 minutes
        • Consider neutron reaction and free neutron half life
  • Further nucleosynthesis in stars
    • No EC process in stars
stellar nucleosynthesis
Stellar Nucleosynthesis
  • He burning
    • 4He+ 4He ↔ 8Be + γ - 91.78 keV
      • Too short lived
    • 3 4He → 12C + γ + 7.367 MeV
    • 12C + 4He →16O
    • 16O + 4He →20Ne
  • Formation of 12C based on Hoyle state
    • Excited nuclear state
      • Somewhat different from ground state 12C
    • Around 7.6 MeV above ground state
    • 0+
stellar nucleosynthesis1
Stellar Nucleosynthesis
  • CNO cycle
    • 12C + 1H →13N + g
    • 13N →13C + e++ νe
    • 13C + 1H →14N + γ
    • 14N + 1H →15O + γ
    • 15O →15N + e+ + νe
    • 15N + 1H →12C + 4He
    • Net result is conversion of 4 protons to alpha particle
      • 4 1H → 4He +2 e++ 2 νe +3 γ
  • Fusion up to Fe
    • Binding energy curve
formation of elements a 60
Formation of elements A>60

Neutron Capture; S-process

  • A>60
  • 68Zn(n, γ) 69Zn, 69Zn → 69Ga+ b- + n
  • mean times of neutron capture reactions longer than beta decay half-life
    • Isotope can beta decay before another capture
  • Up to Bi
nucleosynthesis r process
Nucleosynthesis: R process
  • Neutron capture time scale very much less than - decay lifetimes
  • Neutron density 1028/m3
    • Extremely high flux
    • capture times of the order of fractions of a second
    • Unstable neutron rich nuclei
  • rapidly decay to form stable neutron rich nuclei
  • all A<209 and peaks at N=50,82, 126 (magic numbers)
p process
P process
  • Formation of proton rich nuclei
  • Proton capture process
  • 70
  • Photonuclear process, at higher Z (around 40)
    • (, p), (,), (, n)
    • 190Pt and 168Yb from p process
  • Also associated with proton capture process (p,g)
  • Variation on description in the literature
rp process rapid proton capture
rp process (rapid proton capture)
  • Proton-rich nuclei with Z = 7-26
  • (p,) and + decays that populate the p-rich nuclei
    • Also associated with rapid proton capture process
  • Initiates as a side chain of the CNO cycle
    • 21Na and 19Ne
  • Forms a small number of nuclei with A< 100
review notes
Review Notes
  • Understand Reaction Notation
  • Understand Energetics of Nuclear Reactions
    • Q values and barriers
  • Understand the Different Reaction Types and Mechanisms
    • Particles
    • Energy
  • Relate cross sections to energy
  • Describe Photonuclear Reactions
  • Routes and reactions in nucleosynthesis
  • Influence of reaction rate and particles on nucleosynthesis
  • Describe the different types of nuclear reactions shown on 9-24.
  • Provide notations for the following
    • Reaction of 16O with 208Pb to make stable Au
    • Formation of Pu from Th and a projectile
  • Find the threshold energy for the reaction of 59Co and an alpha that produces a neutron and a product nuclei
  • What are the differences between low and high energy reactions?
  • How does a charged particle reaction change with energy? A neutron reaction?
  • How are actinides made in nucleosynthesis?
  • What is the s-process?
  • What elements were produced in the big bang?
  • Which isotopes are produced by photonuclear reactions?
  • What is interesting about the production of 12C
pop quiz
Pop Quiz
  • Provide the Q value, threshold energy, and Coulomb barrier for the compound nucleus reaction of 18O with 244Cm
  • Provide comment in blog
  • Bring to next class (31 October)
chem 312 lecture 10 chemical speciation
CHEM 312 Lecture 10: Chemical Speciation
  • Use of constants to model chemical form
    • Thermodynamic and kinetic
    • Determine property of radioelement based on speciation
      • Chemical species in system
  • Review
    • Equilibrium constants
    • Activity
    • Use of constants in equation
reaction constants
Reaction Constants
  • For a reaction
    • aA + bB <--> cC + dD
  • At equilibrium ratio of product to reactants is a constant
    • Constant can change with conditions
      • Not particularly constant
    • By convention, constants are expressed as products over reactants
  • Conditions under which the constant is measured should be listed
    • Temperature, ionic strength
complete picture activities
Complete picture: Activities
  • Strictly speaking, activities, not concentrations should be used
  • Activities normalize concentration to amount of anions and cations in solution
  • At low concentration, activities are assumed to be 1
  • constant can be evaluated at a number of ionic strengths and overall activities fit to equations
  • Debye-Hückel (Physik Z., 24, 185 (1923))

ZA = charge of species A

µ = molal ionic strength

RA = hydrated ionic radius in Å (from 3 to 11)

First estimation of activity

  • Debye-Hückel term can be written as:
  • Specific ion interaction theory
    • Uses and extends Debye-Hückel
      • long range Debye-Hückel
      • Short range ion interaction term

ij = specific ion interaction term

  • Pitzer
    • Binary (3) and Ternary (2) interaction parameters
Experimental Data shows change in stability constant with ionic strength

Ion Specific Interaction Theory

Cm-Humate at pH 6





  • Constants can be listed by different names
    • Equilibrium constants (K)
      • Reactions involving bond breaking
        • 2 HX <--> 2H+ + X22-
    • Stability constants (ß), Formation constants (K)
      • Metal-ligand complexation
        • Pu4+ + CO32- <--> PuCO32+
        • Ligand is written in deprotonated form
    • Conditional Constants
      • An experimental condition is written into equation
        • Pu4+ + H2CO3 <--> PuCO32+ +2H+
          • Constant can vary with concentration, pH

Must look at equation!

using equilibrium constants
Using Equilibrium Constants
  • Constants and balanced equation can be used to evaluate concentrations at equilibrium
    • 2 HX <--> 2H+ + X22-
    • K=4E-15
    • If you have one mole of HX initially, what are the concentration of all species at equilibrium?
    • Try to write species in terms of one unknown
      • Start with species of lowest concentration
      • [X22-]=x, [H+]=2x, [HX]=1-2x,
    • Since K is small, x must be small
      • Use the approximation 1-2x ≈ 1
      • Substitute x and rearrange K
    • Solve for x
  • [X22-]=1E-5, [H+]=2E-5
realistic case
Realistic Case
  • Metal ion of interest may be in complicated environment
    • May different species to consider simultaneously
  • Consider uranium in an aquifer
    • Example is still a simplified case
  • Species to consider in this example include
    • free metal ion: UO22+
    • hydroxides: (UO2)x(OH)y
    • carbonates: UO2CO3
    • humates: UO2HA(II), UO2OHHA(I)
  • Need to get stability constants for all species
    • Example: UO22++ CO32- <--> UO2CO3
  • Know or find conditions
    • Total uranium, total carbonate, pH, total humic concentration
stability constants for selected uranium species at 0 1 m ionic strength
Stability constants for selected uranium species at 0.1 M ionic strength

Species logß

UO2 OH+ 8.5

UO2(OH)2 17.3

UO2(OH)3- 22.6

UO2(OH)42- 23.1

(UO2)2OH3+ 11.0

(UO2)2(OH)2+ 22.0

UO2CO3 8.87

UO2(CO3)22- 16.07

UO2(CO3)34- 21.60

UO2HA(II) 6.16

UO2(OH)HA(I) 14.7±0.5

Other species may need to be considered. If total uranium concentration is low enough, binary or tertiary species can be excluded.

Chemical thermodynamics of uranium:

  • Write concentrations in terms of species
  • Total uranium in solution, [U]tot, is the sum of all solution phase uranium species
    • [U]tot= UO22+free+U-carb+U-hydroxide+U-humate
    • [CO32-]free=f(pH)
      • From Henry’s constant for CO2 and K1 and K2 from CO3H2
      • log[CO32-]free=logKHK1K2+log(pCO2)-2log[H+]
        • With -log[H+]=pH
      • log[CO32-]free=logKHK1K2+log(pCO2)+2pH
    • [OH-] = f(pH)
    • [HA]tot = UO2HA + UO2OHHA+ HAfree
uranium speciation equations
Uranium speciation equations
  • Write the species in terms of metal, ligands, and constants
    • Generalized equation, with free uranium, free ligand A and free ligand B
    • Provide free ligand and metal concentrations as pXvalue
      • pX = -log[X]free
      • pUO22+=-log[UO22+]
  • Rearrange equation with pX values
    • Include –logbxab,treat as pX term
    • [(UO2)xAaBb] = 10-(xpUO2+apA+bpB-logxab)
  • Specific example for (UO2)2(OH)22+
    • [(UO2)2(OH)22+]=10-(2pUO2+2pOH-22.0)
  • Set up equations where total solution uranium concentration is sum of all species and solve for known terms
energy terms
Energy terms
  • Constants can be used to evaluate energetic of reaction
    • From Nernst equation
      • ∆G=-RTlnK
    • ∆G=∆H-T∆S
      • -RTlnK = ∆H-T∆S
      • RlnK= - ∆H/T + ∆S
        • Plot RlnK vs 1/T
solubility products
Solubility Products
  • Equilibrium involving a solid phase
    • AgCl(s) <--> Ag+ + Cl-
    • AgCl concentration is constant
      • Solid activity and concentration is treated as constant
      • By convention, reaction goes from solid to ionic phase in solution
    • Can use Ksp for calculating concentrations in solution
solubility calculations
Solubility calculations
  • AgCl(s) at equilibrium with water at 25°C gives 1E-5 M silver ion in solution. What is the Ksp??
    • AgCl(s) <--> Ag+ + Cl-: [Ag+] = [Cl-]
    • Ksp = 1E-52 = 1E-10
  • What is the [Mg2+]from Mg(OH)2 at pH 10?
    • Ksp = 1.2E-11= [Mg2+][OH]2
    • [OH] = 10-(14-10)
solubility calculations1
Solubility calculations
  • Ksp of UO2= 10-52. What is the expected U4+ concentration at pH 6. Generalize equation for any pH
    • Solubility reaction:
      • UO2 + 2 H2OU(OH)4 U4+ + 4 OH-
    • Ksp=[U4+][OH-]4
    • [U4+]=Ksp/[OH-]4
      • pOH + pH =14
      • At pH 6, pOH = 8, [OH-]=10-8
    • [U4+]= 10-52/[10-8]4= 10-52/10-32 = 10-20 M
    • For any pH
      • [U4+]= 10-52/[10-(14-pH)*4]
      • Log [U4+]=-52+((14-pH)*4)
limitations of k sp
Limitations of Ksp
  • Solid phase formation limited by concentration
    • below ≈1E-5/mL no visible precipitate forms
      • colloids
  • formation of supersaturated solutions
    • slow kinetics
  • Competitive reactions may lower free ion concentration
  • Large excess of ligand may form soluble species
    • AgCl(s) + Cl- <--> AgCl2-(aq)

Ksp really best for slightly soluble salts