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Chapter 21 Nuclear Chemistry Nuclear Chemistry Radiocarbon Dating Radioactive C-14 is formed in the upper atmosphere by nuclear reactions initiated by neutrons in cosmic radiation 14N + 1 n ---> 14C + 1H o The C-14 is oxidized to CO2, which circulates through the biosphere. When a plant dies, the C-14 is not replenished. But the C-14 continues to decay with t1/2 = 5730 years. Activity of a sample can be used to date the Nuclear Chemistry sample. Nuclear Medicine: Imaging Thyroid imaging using Tc-99m Nuclear Chemistry 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 Nuclear Chemistry neutrons Food Irradiation •Food can be irradiated with g rays from 60Co or 137Cs. •Irradiated milk has a shelf life of 3 mo. without refrigeration. •USDA has approved irradiation of meats and eggs. Nuclear Chemistry Mass Defect • Some of the mass can be converted into energy • Shown by a very famous equation! 2 E=mc Energy Mass Speed of light Nuclear Chemistry The Nucleus • Remember that the nucleus is comprised of the two nucleons, protons and neutrons. • The number of protons is the atomic number. • The number of protons and neutrons together is effectively the mass of the atom. Nuclear Chemistry Isotopes • Not all atoms of the same element have the same mass due to different numbers of neutrons in those atoms. • There are three naturally occurring isotopes of uranium: Uranium-234 Uranium-235 Uranium-238 Nuclear Chemistry Radioactivity • It is not uncommon for some nuclides of an element to be unstable, or radioactive. • We refer to these as radionuclides. • There are several ways radionuclides can decay into a different nuclide. Nuclear Chemistry Types of Radiation (ά) – a positively charged helium isotope • Alpha 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 4 2 He 0 1 0 0 e g Nuclear Chemistry Penetrating Ability Nuclear Chemistry 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 Nuclear Chemistry Types of Radioactive Decay Nuclear Chemistry Alpha Decay: Loss of an -particle (a helium nucleus) 4 2 238 92 U He 234 90 U + 4 2 He Nuclear Chemistry Beta Decay: Loss of a -particle (a high energy electron) 0 −1 131 53 I 0 or −1 131 54 e Xe + 0 −1 e Nuclear Chemistry Positron Emission: Loss of a positron (a particle that has the same mass as but opposite charge than an electron) 0 1 11 6 C e 11 5 B + 0 1 e Nuclear Chemistry Gamma Emission: Loss of a g-ray (high-energy radiation that almost always accompanies the loss of a nuclear particle) 0 0 g Nuclear Chemistry Electron Capture (K-Capture) Addition of an electron to a proton in the nucleus As a result, a proton is transformed into a neutron. 1 1 p + 0 −1 e 1 0 n Nuclear Chemistry Learning Check What radioactive isotope is produced in the following bombardment of boron? 10B 5 + 4He 2 ? + 1n 0 Nuclear Chemistry Write Nuclear Equations! Write the nuclear equation for the beta emitter Co-60. Nuclear Chemistry Neutron-Proton Ratios • Any element with more than one proton (i.e., anything but hydrogen) will have repulsions between the protons in the nucleus. • A strong nuclear force helps keep the nucleus from flying apart. Nuclear Chemistry Neutron-Proton Ratios • Neutrons play a key role stabilizing the nucleus. • Therefore, the ratio of neutrons to protons is an important factor. Nuclear Chemistry Neutron-Proton Ratios For smaller nuclei (Z 20) stable nuclei have a neutron-to-proton ratio close to 1:1. Nuclear Chemistry Neutron-Proton Ratios As nuclei get larger, it takes a greater number of neutrons to stabilize the nucleus. Nuclear Chemistry Stable Nuclei The shaded region in the figure shows what nuclides would be stable, the socalled belt of stability. Nuclear Chemistry Stable Nuclei • Nuclei above this belt have too many neutrons. • They tend to decay by emitting beta particles. Nuclear Chemistry Stable Nuclei • Nuclei below the belt have too many protons. • They tend to become more stable by positron emission or electron capture. Nuclear Chemistry Stable Nuclei • There are no stable nuclei with an atomic number greater than 83. • These nuclei tend to decay by alpha emission. Nuclear Chemistry Radioactive Series • Large radioactive nuclei cannot stabilize by undergoing only one nuclear transformation. • They undergo a series of decays until they form a stable nuclide (often a nuclide of lead). Nuclear Chemistry Some Trends Nuclei with 2, 8, 20, 28, 50, or 82 protons or 2, 8, 20, 28, 50, 82, or 126 neutrons tend to be more stable than nuclides with a different number of nucleons. Nuclear Chemistry Some Trends Nuclei with an even number of protons and neutrons tend to be more stable than nuclides that have odd numbers of these nucleons. Nuclear Chemistry Nuclear Transformations Nuclear transformations can be induced by accelerating a particle and colliding it with the nuclide. Nuclear Chemistry Particle Accelerators These particle accelerators are enormous, having circular tracks with radii that are miles long. Nuclear Chemistry 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. Nuclear Chemistry Kinetics of Radioactive Decay • Nuclear transmutation is a first-order process. • The kinetics of such a process, you will recall, obey this equation: A = -kt ln A0 Nuclear Chemistry Half-Life Decay of 20.0 mg of 15O. What remains after 3 half- Nuclear Chemistry lives? After 5 half-lives? Kinetics of Radioactive Decay • The half-life of such a process is: 0.693 = t1/2 k • Comparing the amount of a radioactive nuclide present at a given point in time with the amount normally present, one can find the age of an object. Nuclear Chemistry Learning Check! The half life of I-123 is 13 hr. How much of a 64 mg sample of I-123 is left after 39 hours? Nuclear Chemistry Kinetics of Radioactive Decay A wooden object from an archeological site is subjected to radiocarbon dating. The activity of the sample that is due to 14C is measured to be 11.6 disintegrations per second. The activity of a carbon sample of equal mass from fresh wood is 15.2 disintegrations per second. The half-life of 14C is 5715 yr. What is the age of the archeological sample? Nuclear Chemistry Kinetics of Radioactive Decay First we need to determine the rate constant, k, for the process. 0.693 = t1/2 k 0.693 = 5715 yr k 0.693 =k 5715 yr 1.21 10−4 yr−1 = k Nuclear Chemistry Kinetics of Radioactive Decay Now we can determine t: A = -kt ln A0 11.6 −4 yr−1) t ln = -(1.21 10 15.2 ln 0.763 = -(1.21 10−4 yr−1) t 6310 yr = t Nuclear Chemistry Measuring Radioactivity • One can use a device like this Geiger counter to measure the amount of activity present in a radioactive sample. • The ionizing radiation creates ions, which conduct a current that is detected by the instrument. Nuclear Chemistry Effects of Radiation Nuclear Chemistry Nuclear Chemistry Energy in Nuclear Reactions • There is a tremendous amount of energy stored in nuclei. • Einstein’s famous equation, E = mc2, relates directly to the calculation of this energy. Nuclear Chemistry Energy in Nuclear Reactions • In the types of chemical reactions we have encountered previously, the amount of mass converted to energy has been minimal. • However, these energies are many thousands of times greater in nuclear reactions. Nuclear Chemistry Energy in Nuclear Reactions For example, the mass change for the decay of 1 mol of uranium-238 is −0.0046 g. The change in energy, E, is then E = (m) c2 E = (−4.6 10−6 kg)(3.00 108 m/s)2 E = −4.1 1011 J Nuclear Chemistry Nuclear Fission • How does one tap all that energy? • Nuclear fission is the type of reaction carried out in nuclear reactors. Nuclear Chemistry Nuclear Fission • Bombardment of the radioactive nuclide with a neutron starts the process. • Neutrons released in the transmutation strike other nuclei, causing their decay and the Nuclear production of more neutrons. Chemistry Nuclear Fission This process continues in what we call a nuclear chain reaction. Nuclear Chemistry Nuclear Fission If there are not enough radioactive nuclides in the path of the ejected neutrons, the chain reaction will die out. Nuclear Chemistry Nuclear Fission Therefore, there must be a certain minimum amount of fissionable material present for the chain reaction to be sustained: Critical Mass. Nuclear Chemistry Nuclear Reactors In nuclear reactors the heat generated by the reaction is used to produce steam that turns a turbine connected to a generator. Nuclear Chemistry Nuclear Fission & POWER • Currently about 103 nuclear power plants in the U.S. and about 435 worldwide. • 20% of the world’s energy comes from nuclear. Nuclear Chemistry Figure 19.6: Diagram of a nuclear power plant. Nuclear Chemistry Nuclear Reactors • The reaction is kept in check by the use of control rods. • These block the paths of some neutrons, keeping the system from reaching a dangerous supercritical mass. Nuclear Chemistry Nuclear power plants • All power plants produce steam which turns turbines to produce energy. Sources of heat to produce steam: heat from fission, coal, oil, natural gas, water • Nuclear power plant • 1 pellet of U-235 produces as much energy as 149 gallons of oil, 157 gallons gasoline, 1780 pounds of coal • A pellet is about as big as a pencil eraser • One reactor contains 193 assemblies of rods, 260 rods / assembly w/ 230 pellets per rod Nuclear Chemistry 1 million gallons of steam go through the turbine per minute. Turbine spins at 1800 rpm’s. 395,000 gallons of water in the core are heated to 619 F with a pressure of 2235 psi • Every 1.5 years 1/3 of the core is replaced. Takes 40 days to refuel – carried down man made “canals” to a huge swimming pool on site • Standing outside of a containment building you would get 5 milirem exposure of radiation: 10 mrem exposure from x-rays, 15 mrem from 2 Nuclear packs of cigarettes Chemistry Nuclear Fusion • Fusion would be a superior method of generating power. The good news is that the products of the reaction are not radioactive. The bad news is that in order to achieve fusion, the material must be in the plasma state at several million kelvins. Nuclear Chemistry Nuclear Fusion • Tokamak apparati like the one shown at the right show promise for carrying out these reactions. • They use magnetic fields to heat the material. Nuclear Chemistry