Nuclear Chemistry Chapter 23 Radioactivity • One of the pieces of evidence for the fact that atoms are made of smaller particles came from the work of Marie Curie (1876-1934). • She discovered radioactivity, the spontaneous disintegration of some elements into smaller pieces. Nuclear Reactions vs. Normal Chemical Changes • Nuclear reactions involve the nucleus • The nucleus opens, and protons and neutrons are rearranged • The opening of the nucleus releases a tremendous amount of energy that holds the nucleus together – called binding energy • “Normal” Chemical Reactions involve electrons, not protons and neutrons 23.1 Types of Radiation • Alpha (ά) – a positively 4 charged (+2) helium isotope - 2 He we usually ignore the charge because it involves electrons, not protons and neutrons •Beta (β) – an electron •Gamma (γ) – pure energy; called a ray rather than a particle 0 1 0 0 e Other Nuclear Particles • Neutron 1 0 n • Positron – a positive electron 0 1 e •Proton – usually referred to as hydrogen-1 •Any other elemental isotope 1 1 H Penetrating Ability Geiger-Müller Counter 23.7 Geiger Counter • Used to detect radioactive substances Atomic number (Z) = number of protons in nucleus Mass number (A) = number of protons + number of neutrons = atomic number (Z) + number of neutrons Mass Number Atomic Number A ZX Element Symbol proton 1p 1H or 1 1 neutron 1n 0 electron 0b 0e or -1 -1 positron 0b 0e or +1 +1 a particle 4He 4a or 2 2 A 1 1 0 0 4 Z 1 0 -1 +1 2 23.1 Balancing Nuclear Equations 1. Conserve mass number (A). The sum of protons plus neutrons in the products must equal the sum of protons plus neutrons in the reactants. 235 92 U + 10n 138 55 Cs + 96 37 Rb + 2 10n 235 + 1 = 138 + 96 + 2x1 2. Conserve atomic number (Z) or nuclear charge. The sum of nuclear charges in the products must equal the sum of nuclear charges in the reactants. 235 92 U + 10n 138 55 Cs + 96 37 Rb 92 + 0 = 55 + 37 + 2x0 + 2 10n 23.1 212Po decays by alpha emission. Write the balanced nuclear equation for the decay of 212Po. 4 alpha particle - 42He or 2a 212Po 84 4He 2 + AZX 212 = 4 + A A = 208 84 = 2 + Z Z = 82 212Po 84 4He 2 + 208 82Pb 23.1 Nuclear Stability and Radioactive Decay Beta decay +-10b + n 14C 6 14N 7 40K 19 40Ca 20 Decrease # of neutrons by 1 + -10b + n 1n 0 Increase # of protons by 1 1p 1 + -10b + n Positron decay ++10b + n Increase # of neutrons by 1 ++10b + n Decrease # of protons by 1 11C 6 11B 5 38 19K 38Ar 18 1p 1 1n 0 ++10b + n n and n have A = 0 and Z = 0 23.2 Nuclear Stability and Radioactive Decay Electron capture decay +n 37Ar 18 + -10e 37Cl 17 55Fe 26 + -10e 55Mn 25 1p 1 Increase # of neutrons by 1 +n Decrease # of protons by 1 + -10e 1n 0 +n Alpha decay 212Po 84 4He 2 + 208 82Pb Decrease # of neutrons by 2 Decrease # of protons by 2 Spontaneous fission 252Cf 98 1n 2125 In + 2 49 0 23.2 Learning Check What radioactive isotope is produced in the following bombardment of boron? 10B 5 + 4He 2 ? + 1n 0 Learning Check What radioactive isotope is produced in the following bombardment of boron? 10B 5 + 4He 2 13N 7 + 1n 0 Write Nuclear Equations! Write the nuclear equation for the beta emitter Co-60. 60Co 27 0e -1 + 60Ni 28 Artificial Nuclear Reactions New elements or new isotopes of known elements are produced by bombarding an atom with a subatomic particle such as a proton or neutron -- or even a much heavier particle such as 4He and 11B. Reactions using neutrons are called reactions because a ray is usually emitted. Radioisotopes used in medicine are often made by reactions. Artificial Nuclear Reactions Example of a reaction is production of radioactive 31P for use in studies of P uptake in the body. 31 15P + 1 0n ---> 32 15P + Transuranium Elements Elements beyond 92 (transuranium) made starting with an reaction 1 n 0 92U + 239 92U ---> 239 0 b Np + 93 -1 239 Np 93 ---> 239 94Pu + ---> 239 + 238 92U 0 -1b Nuclear Stability • Certain numbers of neutrons and protons are extra stable • n or p = 2, 8, 20, 50, 82 and 126 • Like extra stable numbers of electrons in noble gases (e- = 2, 10, 18, 36, 54 and 86) • Nuclei with even numbers of both protons and neutrons are more stable than those with odd numbers of neutron and protons • All isotopes of the elements with atomic numbers higher than 83 are radioactive • All isotopes of Tc and Pm are radioactive 23.2 Band of Stability and Radioactive Decay Stability of Nuclei • Out of > 300 stable isotopes: N Even Odd Even 157 52 Odd 50 5 Z 19 9F 31 P 15 2 1 H, 63Li, 105B, 147N, 18073Ta Half-Life • HALF-LIFE is the time that it takes for 1/2 a sample to decompose. • The rate of a nuclear transformation depends only on the “reactant” concentration. Half-Life Decay of 20.0 mg of 15O. What remains after 3 half-lives? After 5 half-lives? Kinetics of Radioactive Decay For each duration (half-life), one half of the substance decomposes. For example: Ra-234 has a half-life of 3.6 days If you start with 50 grams of Ra-234 After 3.6 days > 25 grams After 7.2 days > 12.5 grams After 10.8 days > 6.25 grams Kinetics of Radioactive Decay A daughter DA rate = Dt A = A0 (-kt) e lnA = lnA0 - kt A = the amount of atoms at time t A0 = the amount of atoms at time t = 0 k is the decay constant (sometimes called l) t½ = Ln 2 k 0.693 t½ = k 23.3 Radiocarbon Dating 14N 7 + 01n 14C 6 14C 6 14N 7 + 11H + -10b + n t½ = 5730 years Uranium-238 Dating 238U 92 206Pb 82 + 8 24a + 6-10b t½ = 4.51 x 109 years 23.3 Learning Check! The half life of I-123 is 13 hr. How much of a 64 mg sample of I-123 is left after 31 hours? Biological Effects of Radiation Radiation absorbed dose (rad) 1 rad = 1 x 10-5 J/g of material Roentgen equivalent for man (rem) 1 rem = 1 rad x Q Quality Factor -ray = 1 b=1 a = 20 23.8 Effects of Radiation Nuclear Fission Fission is the splitting of atoms These are usually very large, so that they are not as stable Fission chain has three general steps: 1. Initiation. Reaction of a single atom starts the chain (e.g., 235U + neutron) 2. Propagation. 236U fission releases neutrons that initiate other fissions 3. Termination. Nuclear Fission Nuclear Fission 235U 92 + 01n 90Sr 38 1n + Energy + 143 Xe + 3 0 54 Energy = [mass 235U + mass n – (mass 90Sr + mass 143Xe + 3 x mass n )] x c2 Energy = 3.3 x 10-11J per 235U = 2.0 x 1013 J per mole 235U Combustion of 1 ton of coal = 5 x 107 J 23.5 Representation of a fission process. Mass Defect • Some of the mass can be converted into energy • Shown by a very famous equation! E=mc2 Energy Mass Speed of light Nuclear binding energy (BE) is the energy required to break up a nucleus into its component protons and neutrons. BE + 199F 911p + 1010n E = mc2 BE = 9 x (p mass) + 10 x (n mass) – 19F mass BE (amu) = 9 x 1.007825 + 10 x 1.008665 – 18.9984 BE = 0.1587 amu 1 amu = 1.49 x 10-10 J BE = 2.37 x 10-11J binding energy binding energy per nucleon = number of nucleons 2.37 x 10-11 J = 1.25 x 10-12 J = 19 nucleons 23.2 Nuclear binding energy per nucleon vs Mass number nuclear binding energy nucleon nuclear stability 23.2 Nuclear Fission Nuclear chain reaction is a self-sustaining sequence of nuclear fission reactions. The minimum mass of fissionable material required to generate a self-sustaining nuclear chain reaction is the critical mass. Non-critical Critical 23.5 Nuclear Fission & POWER • Currently about 103 nuclear power plants in the U.S. and about 435 worldwide. • 17% of the world’s energy comes from nuclear. Diagram of a nuclear power plant Nuclear Fission Annual Waste Production 35,000 tons SO2 4.5 x 106 tons CO2 3.5 x 106 ft3 ash 1,000 MW coal-fired power plant 70 ft3 vitrified waste 1,000 MW nuclear power plant 23.5 Nuclear Fission Hazards of the radioactivities in spent fuel compared to uranium ore From “Science, Society and America’s Nuclear Waste,” DOE/RW-0361 TG 23.5 Chemistry In Action: Nature’s Own Fission Reactor Natural Uranium 0.7202 % U-235 99.2798% U-238 Measured at Oklo 0.7171 % U-235 Nuclear Fusion Fusion small nuclei combine 2H 1 + 3H 4He 1 2 + 1n + 0 Occurs in the sun and other stars Energy Nuclear Fusion Fusion Reaction 2 2 3 1 1 H + 1H 1 H + 1H 2H 1 + 13H 6Li 3 + 12H 4He 2 2 + 10n 4He 2 Energy Released 6.3 x 10-13 J 2.8 x 10-12 J 3.6 x 10-12 J Tokamak magnetic plasma confinement 23.6 Nuclear Fusion Fusion • Excessive heat can not be contained • Attempts at “cold” fusion have FAILED. • “Hot” fusion is difficult to contain Radioisotopes in Medicine • 1 out of every 3 hospital patients will undergo a nuclear medicine procedure • 24Na, • 131I, t½ = 14.8 hr, b emitter, thyroid gland activity • 123I, t½ = 13.3 hr, ray emitter, brain imaging • 18F, t½ = 1.8 hr, b emitter, positron emission tomography • 99mTc, t½ = 14.8 hr, b emitter, blood-flow tracer t½ = 6 hr, ray emitter, imaging agent Brain images with 123I-labeled compound 23.7 Chemistry In Action: Food Irradiation Dosage Effect Up to 100 kilorad Inhibits sprouting of potatoes, onions, garlics. Inactivates trichinae in pork. Kills or prevents insects from reproducing in grains, fruits, and vegetables. 100 – 1000 kilorads Delays spoilage of meat poultry and fish. Reduces salmonella. Extends shelf life of some fruit. 1000 to 10,000 kilorads Sterilizes meat, poultry and fish. Kills insects and microorganisms in spices and seasoning.