Chapter 24 Nuclear Chemistry 24.1 Nuclear Radiation 24.2 Radioactive Decay (includes decay rates & radiochemical dating) 24.3 Nuclear Reactions (Transmutation Part only) 24.4 Applications & Effects of Nuclear Reactions (except for radiation dose and intensity/distance) Section 24.1 Nuclear Radiation Under certain conditions, some nuclei can emit alpha, beta, or gamma radiation. • Summarize the developments that led to the discovery and understanding of nuclear radiation, including the names of the important scientists and the nature and significance of their contributions. • Distinguish between chemical and nuclear reactions. • Identify alpha, beta, and gamma radiations in terms of composition and key properties. • Rank the penetrating power of the various types of radiation. • Predict the effect of an electric field on the path of the various types of radiation. Section 24.1 Nuclear Radiation Key Concepts • Wilhelm Roentgen discovered X rays in 1895. • Henri Becquerel, Marie Curie, and Pierre Curie pioneered the fields of radioactivity and nuclear chemistry. • Gamma radiation has the most and alpha particles the least penetrating power of the 3 basic types of nuclear radiation. Chemical vs Nuclear Reactions Chemical Nuclear Bonds broken & formed Nuclei emit particles and/or rays Atoms remain Atoms often changed unchanged – may be into atoms of new rearranged or ionized element Involve only valence May involve protons, electrons neutrons, & electrons Small energy changes Large energy changes Chemical vs Nuclear Reactions Chemical Reaction rate influenced by temperature, pressure, concentration, and catalysts Nuclear Rate not normally affected by temperature, pressure, or catalysts Classifying Classify each of the following as a chemical reaction, a nuclear reaction, or neither: ? • Thorium emits a beta particle Nuclear • Two atoms share electrons to form a Chemical bond • A sample of pure sulfur releases heat as Neither it slowly cools • A piece of iron rusts Chemical Discovery of Radioactivity Wilhelm Roentgen (Germany), 1895: invisible rays emitted when electrons bombarded surface of certain materials Rays caused photographic plates to darken Roentgen called these high energy rays called X rays Roentgen in 1901 became first Nobel laureate in physics for this discovery Discovery of Radioactivity Antoine-Henri Becquerel 1896 (France) experiment to determine if phosphorescent minerals also gave off X-rays Image of Becquerel's photographic plate which has been fogged by exposure to radiation from a uranium salt. The shadow of a metal Maltese Cross placed between the plate and the uranium salt is clearly visible. http://en.wikipedia.org/wiki/Henri_Becquerel Discovery of Radioactivity Becquerel discovered that certain minerals were constantly producing penetrating energy rays he called uranic rays • like X-rays, but not related to fluorescence Determined that • all minerals that produced these rays contained uranium • rays were produced even though mineral was not exposed to outside energy Energy apparently being produced from nothing?? Discovery of Radioactivity Henri Becquerel uranium salt K2UO2(SO4)2 Darkened photographic plates– even when not exposed to light – Discovery of Radioactivity Marie Curie (Polish born French physicist/chemist) ~ 1896-1898 Named process by which materials give off such rays radioactivity Emitted rays and particles she named radiation Developed device to measure radioactivity Detecting Radiation: Electroscope When When exposed positively to ionizing charged, radiation, metal radiation knocks foils in electrons electroscope off airspread molecules, apartwhich due tojump onto foils andlike discharge charge repulsion them, causing them to drop down Madam Curie Used electroscope to detect uranic rays in samples Discovered new elements by detecting their rays • radium named for its green phosphorescence • polonium named for her homeland Since these rays were no longer just a property of uranium, she changed name from uranic rays to radioactivity Discovery of Radioactivity Curies in 1898, by processing several tons of uranium ore (pitchblende), identified 2 new radioactive elements: polonium, radium Curies shared 1903 Nobel prize in physics with Becquerel Marie awarded 1911 Nobel prize in chemistry for work with polonium & radium Died in 1934 from effects of radiation Discovery of Radioactivity Name, Date Contribution Wilhelm Discovery of X-Rays Roentgen, 1895 Henri Becquerel, Uranium salt darkens 1896 photographic plate Marie Curie, 1896-1898 (up to 1934) Pierre & Marie Curie, 1898 Introduced terms radioactivity & radiation; developed device to measure radioactivity Isolated polonium and radium & continued study of radiation Properties of Radioactivity Can ionize matter (cause uncharged matter to become charged) • basis of Geiger Counter and electroscope Has high energy Can penetrate matter Causes phosphorescent materials to glow • basis of scintillation counter 3 Common Types of Radiation Alpha particles Beta particles Gamma rays (two more types described in next section) Alpha Radiation Alpha particle 4 He+2 2 • 2 protons & 2 neutrons = nucleus of helium-4 atom • +2 charge + Beta Radiation 0 b -1 Beta particles – fast moving electrons Originate from decay of a neutron + b Beta Decay In Neutron neutron Particle Symbol proton Relative mass Electron e1/1840 Proton p+ 1.000 W– boson Neutron n0 1.001 Matter changed to energy plus other matter neutrino electron Neutron (made of quarks - fundamental) does not Example of weak force, of which W– is a boson “contain” an electron (a lepton) Gamma Radiation 0 g 0 High energy radiation; massless Except for very unusual cases, gamma radiation always accompanies alpha and beta decay – few “pure” gamma emitters Characteristics of Alpha, Beta, and Gamma Radiation Alpha, Beta, Gamma Properties Particle Energy alpha ~5 MeV beta gamma Penetrating Power Blocked by paper 0.05 to Blocked by thin metal foil 1 MeV (aluminum foil) ~1 MeV Blocked only by thick layers of lead or concrete Penetrating Ability of Radioactive Rays a g b 0.01 mm 1 mm 100 mm Thickness of Lead Effect of Electric Field on Trajectory of Subatomic Particles Lead Block Hole Positive plate b 1charge g 0 charge Radioactive Source a 2+ charge Negative plate X-Rays Not generated by nuclear processes (get by bombarding materials with electrons) Like gamma rays – form of high energy electromagnetic radiation (gamma has higher energy) Both X and gamma rays highly penetrating & can be very damaging to living tissue Practice Nuclear Radiation Problems 1-5, page 864 Problems 34-41, page 894 Chapter 24 Nuclear Chemistry 24.1 Nuclear Radiation 24.2 Radioactive Decay (includes decay rates & radiochemical dating) 24.3 Nuclear Reactions (Transmutation Part only) 24.4 Applications & Effects of Nuclear Reactions (except for radiation dose and intensity/distance) Section 24.2 Radioactive Decay Unstable nuclei can break apart spontaneously, changing the identity of atoms. • Explain why certain nuclei are radioactive while others are stable. • Predict the type of radiation an unstable nucleus will emit. • Apply your knowledge of radioactive decay to write balanced nuclear equations. • Solve problems involving radioactive decay rates. • Explain the basis for the technique of radiochemical dating, especially carbon dating. • Describe the decay processes of positron emission and electron capture. Section 24.2 Radioactive Decay Key Concepts • Radioisotopes emit radiation to attain more-stable atomic configurations. • Atomic number and mass number are conserved in nuclear reactions. • Radiochemical dating is a technique for determining the age of an object by measuring the amount of certain radioisotopes remaining in the object. Section 24.2 Radioactive Decay Key Concepts • A half-life is the time required for half of the atoms in a radioactive sample to decay. The number of nuclei N remaining after a certain number of half-lives n or after some time t can be calculated from: Nuclear Reactions Involve a change in atom’s nucleus Radioactive materials spontaneously emit radiation • Called radioactive decay • Do this because a radioactive nucleus is unstable Gain stability by losing energy Pencil Analogy for Stability Gravitational Potential Energy Forces Between Nucleons Green: Strong Force (attractive) Purple: EM Force (repulsive for protons) Nuclear Stability - Forces Nucleons (protons, neutrons) held together by strong force Overcomes electrostatic repulsion by protons Neutrons don’t have repulsion Stability tied to neutron/proton ratio (n/p) High atomic number nuclei need relatively more neutrons for stability Range for stable nuclei: 1:1 light to 1.5:1 heavy (Pb, AN 82) Neutron-toProton Ratio Shaded region corresponds to “band” or “belt” of stability Nuclear Stability Radioactive nuclei are found outside band of stability – above/below/beyond Undergo decay to gain stability All elements with atomic number (AN) > 82 (lead) are radioactive Isotopes of elements with AN ≤ 82 but outside band of stability are radioactive Nuclear Stability – Decay Series Various decay types change n/p in different ways Unstable nuclei lose energy through radioactive decay in order to form a nucleus with a stable n/p ratio Eventually, radioactive atoms undergo enough decays to form stable atoms • Lead-206 is final decay product of Uranium-238 (14 steps) Decay of 238U to 206Pb Practice Nuclear Stability Problems 12 - 14 page 874 Problems 42, 45 – 48, 50 page 894 Nuclear Equations Atomic number (AN) and mass numbers (MN) are shown Atomic and mass numbers are conserved AN: 88 = 86 +2 MN: 226 = 222 + 4 5 Types of Radiation Alpha Beta Positron Emission * Electron Capture * Gamma * New in this section Alpha Radiation Alpha particle emission changes the element Leaves n/p about the same (for heavier elements) In example below, start with radium, end up with radon n/p: 138/88=1.57 136/86 =1.58 Beta Radiation 0 b -1 Beta particles – fast moving electrons Originate from decay of neutron Beta emission changes element Lowers n/p In example below, start with carbon, end up with nitrogen n/p: 8/6=1.43 7/7 =1.00 Positron Emission (b+ Decay) Positron Emission + (b Decay) Neutron-deficient isotopes can decay by proton decay (emitting positrons – antiparticle of electron) + anti-neutrino + + + + + + + + + Net effect: one proton replaced by positron • neutron • anti-neutrino • positron Electron Capture Like positron emission, also reduces number of protons (increase n/p) Nucleus draws in surrounding electron (usually from lowest energy level) Electron combines with proton to form neutron with X-ray emission 1 p + 0 e 1 n + X-ray 1 -1 0 81 Rb 37 + 0-1e 8136Kr + X-ray Decay Processes that Increase n/p Positron Emission Electron Capture + b Particle Changes Beta Emission: neutron proton 1 0 n p b 1 1 0 1 Positron Emission: proton neutron 1 1p 1 0 0 n 1b Electron Capture: proton neutron 1 1p 0 -1e 1 0n Decay Process Summary Decay alpha beta Positron Emission Electron Capture gamma Particle Mass # Change AN Change 2He -4 -2 -1b 0 +1 1b 0 -1 X-Ray Photon 0 -1 0g 0 0 4 0 0 0 Nuclear Equations Atomic number (AN) and mass numbers (MN) are shown Atomic and mass numbers are conserved AN: 88 = 86 +2 MN: 226 = 222 + 4 Nuclear Equations 60 Co 27 6028Ni + ? Conserve mass number: 60 = 60 + 0 Conserve atomic number: 27 = 28 + (-1) Particle must be 0-1b 241 Am 95 23793Np + ? Conserve mass number: 241 = 237 + 4 Conserve atomic number: 95 = 93 +2 Particle must be 42He Practice: Write Nuclear equation for each of Following Alpha emission from U-238 238 92 U He 4 2 234 90 Th Beta emission from Ne-24 24 10 Ne b 0 -1 24 11 Na 13 6 C Positron emission from N-13 13 7 Electron capture by Be-7 7 4 N b 0 1 Be e Li 0 1 7 3 Practice Writing & Balancing Nuclear Equations Problems 6 - 8 page 869 Problems 51 - 54, page 894 Half Life Time for ½ of radioisotope in sample to undergo nuclear decay Half life remains constant In 7 half lives, <1% of original radioactivity remains ½½½½½½½ =1/27 = 1/128 = 0.8% Decay of Strontium-90 Half Life General expression for remaining material after an integer number (n) of half-lives have passed (page 871, text) Remaining (N) = Initial Amount (N0) (1/2)n If value of half life = T & elapsed time = t (both quantities in same units of time) Remaining (N) = Initial Amount (N0) (1/2)t/T Expression works for non-integer t/T t/T = 1.5, (1/2)1.5 = 0.354 Has form of exponential decay function Exponential Decay If value of half life = T & elapsed time = t (both quantities in same units of time) N = N0 (1/2)t/T Expression works for non-integer t/T Define decay parameter = T ln(0.5) ln(0.5) = 0.693 Then equivalent expression to above is N= N0 e-t/ More typical form for expressing decay Half Lives of Radon (Rn) Same element; isotopes have different half lives (more stable as n/p ratio becomes closer to ideal) Isotope Rn-217 Rn-218 Rn-219 Rn-220 Rn-212 Rn-211 Rn-222 Half Life 0.6 milliseconds 35.0 milliseconds 3.96 seconds 55.6 seconds 24.0 minutes 14.6 hours 3.82 days Half Life Reflects Stability Isotope Ra-216 C-15 Ra-224 I-125 C-14 U-238 Te-128 Half life <0.2 nsec (shortest, spin dependent) 2.4 sec 3.6 days 60 days 5730 years 4.5x109 years 7.7x1024 years (longest) Practice Radioactive Decay Problems 16 – 17*, page 874 Problems 55 – 58*, page 895 Problems 4 - 6, page 991 * Problems 17, 57 & 58 require knowing that: if c = ab then log(c) = b log(a) Radiochemical Dating Nuclear decay rates not affected by temperature, pressure, concentration, catalyst Can take advantage of constancy of half-life to date objects Carbon dating commonly used to measure age of objects that were once living - based on radioactive carbon-14 Other nuclei also useful for specialized dating applications Isotopes Useful in Radioactive Dating t1/2 Isotope (years) Useful Range (years) Applications H-3 12.3 1 to 100 Aged wines Pb-210 22 1 to 75 Skeletal remains C-14 5730 500 to 50,000 Organic material K-40 1.3x109 U-238 4.5x109 Re-187 4.3x1010 104 to oldest Earth Earth & moon’s samples crust 107 to oldest Earth Earth’s crust samples 4x107 to oldest Meteorites samples in universe Radiocarbon Dating % C-14 (compared to living organism) Object’s Age (in years) 100% 90% 80% 60% 50% 40% 25% 10% 5% 1% 0 870 1850 4220 5730 7580 11,500 19,000 24,800 38,100 14C Dating Overview C-14 Formation Process Cosmic ray protons blast nuclei in upper atmosphere, producing large variety of particles (including neutrons) Top of Atmosphere Cosmic ray proton collides with nucleus in atmosphere Neutron C-14 Formation Process These neutrons in turn bombard nitrogen (major constituent of atmosphere) Absorption of neutron by N-14 causes it to emit a proton, forming radioactive isotope C-14 Carbon-14 Formation Rate Fairly constant over time C-14 dating calibrated against tree rings so formation rate variations and other factors that affect C-14 to C-12 ratio (other than C14 decay) have, in principle, been corrected for 14C 14C combines with oxygen to become C-14 labeled carbon dioxide 14C becomes part of natural carbon cycle - becomes incorporated into organisms Dating Living organism continues to take in 14C while simultaneously 14C decays When it dies 14C continues to decay without being replenished 14C dating measures time of death 14C Dating Radiocarbon Dating Summary Based on radioactive carbon-14 C-14 formed in upper atmosphere from nitrogen at ~ constant rate percent of C-14 in atmosphere ~ fixed Living organism exchanges CO2 with atmosphere and ingests other carbon compounds (e.g. carbohydrates) Living organism has fixed % of C-14 in all carbon containing molecules present Radiocarbon Dating Summary Living organism has fixed % of C-14 in all carbon containing molecules present Upon death of organism, supply of new C14 stops C-14 already present decays 14 C 14 N + 0 b ½ life = 5730 yrs 6 7 -1 Amounts of stable C-12 & C-13 remain unchanged Measuring C-14 / (C-12 + C-13) in sample and comparing to atmosphere gives age Practice Radiochemical Dating Problem 18, page 874 Chapter 24 Nuclear Chemistry 24.1 Nuclear Radiation 24.2 Radioactive Decay (includes decay rates & radiochemical dating) 24.3 Nuclear Reactions (Transmutation Part only) 24.4 Applications & Effects of Nuclear Reactions (except for radiation dose and intensity/distance) Section 24.3 Nuclear Reactions Fission, the splitting of nuclei, and fusion, the combining of nuclei, release tremendous amounts of energy. • Describe the transmutation process and its role in the development of new isotopes and elements. ========================================== Section 24.3 Nuclear Reactions Key Concepts • Induced transmutation is the bombardment of nuclei with particles in order to create new elements. • These particles can be other nuclei, neutrons or protons. ========================================== Transmutation All natural radioactive processes except gamma emission involve transmutation – conversion of atom of one element to an atom of another element Above is natural or spontaneous transmutation Can have induced transmutation by bombarding nuclei with particles All transuranium elements created this way Transmutation Particles used in bombardment include: Neutrons Protons Charged nuclei of other elements Transmutation reactions also can produce neutrons and protons as products (not seen in natural radiation processes) Transmutation First induced transformation by E. Rutherford, 1919, using alpha particles + + Transmutation What element is produced? ? 22 Ne + 244 Am 266 10 95 105Db (Dubnium) Transuranium Elements All elements following uranium on periodic table (AN>92) All are synthetic elements – produced in lab by induced transmutation First discovered in 1940, neptunium (Np) and plutonium (Pu) produced by bombarding U-238 with neutrons 238 U 92 + 10n 23992U 23993Np + 0-1b 239 Np 239 Pu + 0 b 93 94 -1 Transmutation If particle used to bombard nucleus has + charge (common), need high-velocity (high energy) to overcome charge repulsion with positively charged nucleus High energy created in particle accelerators Success in producing a somewhat stable new nucleus depends on obtaining favorable neutron to proton ratio Practice Induced Transmutation Problems 19 - 21, page 876 Problems 59, 69 - 71, page 895 Chapter 24 Nuclear Chemistry 24.1 Nuclear Radiation 24.2 Radioactive Decay (includes decay rates & radiochemical dating) 24.3 Nuclear Reactions (Transmutation Part only) 24.4 Applications & Effects of Nuclear Reactions (except for radiation dose and intensity/distance) Section 24.4 Applications and Effects of Nuclear Reactions Nuclear reactions have many useful applications, but they also have harmful biological effects. • Name and describe several methods used to detect and measure radiation. • Name and describe several non-medical applications of radiation • Describe and explain several ways that radiation is used to diagnose and to treat disease. • Describe some of the damaging effects of radiation on biological systems and how it can be used as an advantage in the treatment of disease. Section 24.4 Applications and Effects of Nuclear Reactions Key Concepts • Different types of counters are used to detect and measure radiation. • Radiotracers are used to diagnose disease and to analyze chemical reactions. Detecting Radiation Effect of radiation on photographic film similar to effect of light Film used to provide quantitative measure of radioactivity Common implementation is film badge Detecting Radiation Geiger Counter Ionizing radiation – energetic enough to ionize matter with which it collides Geiger counter responsive to ionizing radiation Detecting Radiation Scintillation Counter Detects bright flashes of light with photodetector when ionizing radiation excites electrons of certain types of atoms Detecting Radiation Luminous dials information I Luminous dials information II Scintillation counter uses phosphor-coated surface to detect radiation Scintillations = bright flashes of light Number & brightness of scintillations can be detected & recorded by a variety of sensors sensitive to light Nonmedical Uses of Isotopes Smoke detectors Am-241 produces a radiation to ionize air Smoke blocks ionized air, breaks circuit Insect control - sterilize males Food preservation Smoke Detector http://www.howstuffworks.com/inside-smoke.htm Ionization Chamber with radioactive Am-241 source Electronic Horn Agricultural Application Solution of phosphate, with radioactive P-32, injected into root system of plant P-32 behaves identically to P31 (common, non-radioactive form of element) and is used by plant in same way Geiger counter detects movement of P-32; information used to understand detailed mechanism of how plants utilize P to grow and reproduce Radiation - Medical Applications Tracers Imaging (use radiation to detect features inside the body) Therapy (radiation put into body to kill targeted cells) Medical Radiotracers Radioactive isotopes of an element have same chemical properties as nonradioactive isotopes Certain organs absorb most or all of a particular element Isotopes also can be bound in chemical structure that targets particular organs Tracers used to track distribution & breakdown of substance in body Some Medical Radiotracers Nuclide Iodine-131 Iron-59 Molybdenum-99 Phosphorus-32 Strontium-87 Technetium-99 Half-life 8.1 days 45.1 days 67 hours 14.3 days 2.8 hours 6 hours Organ/System thyroid red blood cells metabolism eyes, liver bones heart, bones, liver, lungs Radioactivity must be able to leave body and be detected – gamma is preferred, alpha totally useless Bone Scans Positron Emission Tomography Cyclotron generated positron (01b) emitting isotopes with short half lives: C-11 (~20 min), N13 (~10 min), O-15 (~2 min), and F-18 (~110 min) 18 F 9 01b + 188O 0 e = 2 g b + 1 -1 0 (positron emission) (matter/anti-matter annihilation) Isotopes incorporated into compounds normally used by body such as glucose, water or ammonia Injected into body - trace where they are distributed (radiotracers) Positron Emission Tomography FDG taken up by highglucose-using cells such as brain, kidney, and cancer cells Oncology scans using FDG make up over 90% of all PET scans in current practice Positron + (b ) Decay Nucleus Neutrons 18F-FDG + + + Protons Electrons Positron Annihilation Annihilation of positron (antimatter) when it encounters an electron (matter) gives • 2 x g rays (180 degrees apart) • Line of response Scanner: photon counter • Counts gamma-ray pairs vs. single gammas • Time window ~ 1 ns 511 keV e+ e511 keV PET Imaging Overview Synthesize radiotracer Inject radiotracer Measure gammaray emissions from isotope (~20-60 min) Reconstruct images of radiotracer distribution Positron Emission Tomography Scintillator (detects pair of light bursts from passage of x g photons) Positron-electron annihilation to produce opposite g photons Coincidence Processing Unit Image Reconstruction Radiotherapy Cancer treatment - cancer cells more sensitive to radiation than healthy cells – can be destroyed by radiation treatment Options include: • place radioisotope directly at site of cancer • use radiation from outside body • use radioisotopes that naturally concentrate in one area of body Gamma Knife System One advanced application of g rays: successful treatment of brain tumors Delivers precise beams of radiation to diseased brain tissue or tumor from large number of directions - 201 beams of radiation intersect on targeted area of abnormal or cancerous tissue within brain Very precise: damages and destroys unhealthy tissue while sparing adjacent normal, healthy brain tissue Gamma Knife Treatment 201 small cobalt sources (gamma) arrayed in hemisphere within thickly shielded structure Energy focused into overlapping beams by collimators Beams focused on target through metal helmet, in which patient’s head is placed by using fixation of head frame attached to head Gamma radiation at focal point of collimators extremely intense Gamma Knife Treatment Gamma Ray Treatment Practice Radiation detection and uses Problems 28, 29, 31, page 890 Problems 73, 75, page 895