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Nuclear Reactions and Their Applications Review • • • • • • Atomic Number (Z) – number of protons Mass Number (A) – sum of protons and neutrons Z + N = A (mass number of nuclide) Protons (Z) + Neutrons (N) = Nucleons Nuclide: a nucleus with a particular composition Most elements occur in nature as a mixture of isotopes (characteristic number of protons but different number of neutrons) Radioactive Decay • Nucleus undergoes decomposition to form a different nucleus. Radioactive Stability • • • • • Nuclides with 84 or more protons are unstable. Light nuclides are stable when Z equals A – Z (neutron/proton ratio is 1). For heavier elements the neutron/proton ratio required for stability is greater than 1 and increases with Z. Certain combinations of protons and neutrons seem to confer special stability. – Even numbers of protons and neutrons are more often stable than those with odd numbers. Certain specific numbers of protons or neutrons produce especially stable nuclides. – 2, 8, 20, 28, 50, 82, and 126 - magic numbers It parallels for atoms where 1, 10, 18, 36, 54 and 86 electrons produce chemical stability Noble gases Red dots indicate stable nuclides As the number of protons in a nuclide increases the proton-to-neutron ratio Required for stability also increases Types of Radioactive Decay • Alpha production (α): • Beta production (β): • Gamma ray production (γ): • Positron production: • Electron capture: Inner-orbital electron Three types of radioactive emissions in an electric field. + Gamma emission: involves the radiation of high-energy γ photons from an excited nucleus. Gamma rays usually result from a particle and an anti-particle annihilation. 0 1 β + −10 e → 2 00γ Balancing Nuclear Equations TotalA TotalZ Reactants= TotalA TotalZ Products Write balanced equations for the following nuclear reactions: (a) Naturally occurring thorium-232 undergoes α decay. (b) Zirconium-86 undergoes electron capture. PLAN: SOLUTION: Write a skeleton equation; balance the number of neutrons and charges; solve for the unknown nuclide. (a) 232 90Th 228 88X + 4 232 A = 228 and Z = 88 (b) 8640Zr + 0-1e → A = 86 and Z = 39 2α A 90Th ZX 8640Zr + 0-1e → 228 → 88Ra 86 + 39Y 4 2α Predicting the Mode of Decay Neutron-rich nuclides undergo β decay. Neutron-poor nuclides undergo positron decay or electron capture. Heavy nuclides undergo α decay. Which of the following nuclides would you predict to be stable and which radioactive? Explain. (a) 18 10Ne (b) 32 16S (c) 236 90Th (a) N/Z = 0.8; there are too few neutrons to be stable - radioactive (b) N/Z = 1.0; Z < 20 and N and Z are even - stable (d) 123 56Ba (c) Every nuclide with Z > 83 is radioactive. (d) N/Z = 1.20; zone of stability figure shows stability when N/Z ≥ 1.3. - radioactive Predicting the Mode of Nuclear Decay PROBLEM: Use the atomic mass of the element to predict the mode(s) of decay of the following radioactive nuclides: (a) PLAN: 12 5B (b) 234 92U (c) 81 33As (d) 127 57La Find the N/Z ratio and compare it to the band stability. Then predict which of the modes of decay will give a ratio closer to the band. SOLUTION: (a) N/Z = 1.4 which is high. The nuclide will probably undergo β− decay altering Z to 6 and lowering the ratio. (c) N/Z = 1.24 which is in the band of stability. It will probably undergo β− decay or positron emission. (b) The large number of neutrons makes this a good candidate for α decay. (d) N/Z = 1.23 which is too low for this area of the band. It can increase Z by positron emission or electron capture. The 238U decay series. Rate of Decay • The rate of decay is proportional to the number of nuclides. This represents a first-order process. Half - Life ∆N Rate = kN − = ∆t ln N = −kt No • Time required for the number of nuclides to reach half the original value. t1/ 2 = ln ( 2 ) 0.693 = k k Large k means a short half-life and vice versa SI unit of decay is the becquerel (Bq) = 1 d/s. curie (Ci) = number of nuclei disintegrating each second in 1 g of radium-226 = 3.70 x 1010 d/s The decay of a 10.0-g sample of strontium-90 over time. Note that the half-life is a constant 28.8 years. Decrease in the number of 14C nuclei over time. Carbon–14 Dating Applying Radiocarbon Dating PROBLEM: PLAN: The charred bones of a sloth in a cave in Chile represent the earliest evidence of human presence in the southern tip of South America. A sample of the bone has a specific activity of 5.22 disintegrations per minute per gram of carbon (d/min•g). If the 12C/14C ratio for living organisms results in a specific activity of 15.3 d/min•g, how old are the bones (t1/2 of 14C = 5730 yr)? Calculate the rate constant using the given half-life. Then use the first-order rate equation to find the age of the bones. SOLUTION: k= ln 2 = t1/2 1 t= ln k 0.693 = 1.21 x 10-4 yr -1 5730 yr 1 A0 = ln 1.21 x 10-4 yr -1 At The bones are about 8900 years old. 15.3 5.22 = 8.89 x 103 yr PROBLEM: Strontium-90 is a radioactive byproduct of nuclear reactors that behaves biologically like calcium, the element above it in Group 2A(2). When 90Sr is ingested by mammals, it is found in their milk and eventually in the bones of those drinking the milk. If a sample of 90Sr has an activity of 1.2 x 1012 d/s, what are the activity and the fraction of nuclei that have decayed after 59 yr (t1/2 of 90Sr = 29 yr). The fraction of nuclei that have decayed is the change in the number of nuclei, expressed as a fraction of the starting number. The activity of the sample (A) is proportional to the number of nuclei (N). We are given the A0 and can find At from the integrated form of the first-order rate equation. t1/ 2 0.693 −1 ln ( 2 ) 0.693= k 0.024 yr = = = 29 yr k k ln At = -kt + ln A0 At = 2.9 x ln At = -(0.024 yr -1)(59 yr) + ln(1.2 x 1012 d/s) 1011 d/s Fraction decayed Fraction decayed = 0.76 = ln At = 26.4 (1.2 x1012 - 2.9 x 1011) (1.2 x 1012) Nuclear Transformation • The change of one element into another. 27 13 1 Al + 24 He → 30 P + 15 0n Linear accelerator Cyclotron accelerator. 249 98 263 Cf + 188 O → 106 Sg + 4 01 n Nuclear Fission and Fusion • Fusion – Combining two light nuclei to form a heavier, more stable nucleus. • Fission – Splitting a heavy nucleus into two nuclei with smaller mass numbers. 1 0 n+ 235 92 U→ 142 56 Ba + 91 36 1 0 Kr + 3 n 18 The Interconversion of Mass and Energy E = mc2 ∆E = ∆mc2 ∆E ∆m = 2 c The mass of the nucleus is less than the combined masses of its nucleons. The mass decrease that occurs when nucleons are united into a nucleus is called the mass defect. The mass defect (∆m) can be used to calculate the nuclear binding energy in MeV (mega-electron volts). 1 amu = 931.5 x 106 eV = 931.5 MeV Energy and Mass When a system gains or loses energy it also gains or loses a quantity of mass. • E = mc2 Δm = mass defect ΔE = change in energy • If ΔE is negative (exothermic), mass is lost from the system. Calculating the Binding Energy per Nucleon PROBLEM: Iron-56 is an extremely stable nuclide. Compute the binding energy per nucleon for 56Fe and compare it with that for 12C (mass of 56Fe atom = 55.934939 amu; mass of 1H atom = 1.007825 amu; mass of neutron = 1.008665 amu). Find the mass defect, ∆m; multiply that by the MeV equivalent and divide by the number of nucleons. PLAN: SOLUTION: Mass Defect = [(26 x 1.007825 amu) + (30 x 1.008665 amu)] - 55.934939 ∆m = 0.52846 amu Binding energy = 12C (0.52846 amu)(931.5 MeV/amu) 56 nucleons = 8.790 MeV/nucleon has a binding energy of 7.680 MeV/nucleon, so 56Fe is more stable. Binding Energy • • The energy required to decompose the nucleus into its components. Iron-56 is the most stable nucleus and has a binding energy of 8.79 MeV. Biological Effects of Radiation Depend on: 1. 2. 3. 4. Energy of the radiation Penetrating ability of the radiation Ionizing ability of the radiation Chemical properties of the radiation source Penetrating power of radioactive emissions Penetrating power is inversely related to the mass and charge of the emission. Nuclear changes cause chemical changes in surrounding matter by excitation and ionization. rem (roentgen equivalent for man) • The energy dose of the radiation and its effectiveness in causing biologic damage must be taken into account. Number of rems = (number of rads) × RBE sievert (Sv), 1 Sv = 0.01 rem rads = radiation absorbed dose Gray (Gy) SI unit of dose RBE = relative effectiveness of the radiation in causing biologic damage Rad = 0.01 J/kg=0.01 Gy 25 Effects of Short-Term Exposures to Radiation DNA Damage by High Energy Radiation Radiation-induced DNA damage can lead to mutagenesis and cancer PHOTODIMERIZATION: Pyrimidine dimerization causes skin cancer O O O CH3 N CH3 CH3 N N hv 2 O O N N R R H H N O R PHOTOIONIZATION MECHANISMS Indirect Photoionization Damage: Attack of DNA by OH. in dilute aqueous solutions results in strand breaks and modification of nucleotide bases (γ radiolysis) Strand-base +nhν → strand-base+. + e-aq 2H2O + nhν → 2H++OH. + OHOH. + strand-base → strand-base.-OH strand-base.-OH → ssb and base release Direct Photoionization Damage: Direct ionization of DNA by high energy radiation Aqueous base (B1) ionization energies and orbital diagrams for 5'-dGMP-, 5'-dAMP-, 5'-dCMP-, 5'-dTMP-, 2'deoxythymidine and uridine P.R. LeBreton, Papadantonakis, G.A. et al Proc. Natl. Acad. Sci. USA (1998) 95, 5550-5555 After consumption of Na 131I, the patient's thyroid is scanned for radio- activity levels to determine the efficiency of iodine absorption.