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Unformatted text preview: Chapter 21 Nuclear ChemistryNuclear chemistry involves changes in the nuclear composition of atoms that are radioactive.Nuclear ChemistryMany applications Source of energy Medical diagnosis and treatment Carbon dating1221.1 RadioactivityWhy do the elements occur in widely different amounts in the universe? H  91%Radioactivity90 elements exist naturally on Earth 81 of these have at least one stable isotope PoU have no stable isotopes (radioactive) PoThe heavier elements (Np  ) are synthetic (Np and radioactive.(HBi, except for 43Tc and 61Pm) (H34RadioactivityNot all isotopes are equally stable  the radioactive ones undergo nuclear decay to form other elements.RadioactivityWhen discussing nuclear reactions, we are interested in specific nucleons (particles in the nucleus)  protons and neutrons  which provide the majority of the mass of the nucleus.5 611RadioactivityZ = atomic number = # protons N = neutron number = # neutrons A = Z + N = mass number = # nucleons nuclide = nucleus of an isotope symbol: AZE Only 264 of the 1700 known nuclides are stable; the others decompose spontaneously at some characteristic rate, emitting some type of radiation.7RadioactivityReview How many protons and neutrons are in the following nuclides?14 C 6 18OUranium235 Uranium8Nuclear EquationsRadiation arises from nuclear reactions:parent nuclide daughter nuclide + radiationNuclear EquationsTypes of emission particles Alpha Particles: 42He or 42 Beta Particles: 01e or 01 0 e or 0 Positrons: +1 +1 Gamma Rays: (no mass or charge)To balance, two conditions must be met: 1 Conserve mass number(A), the #of nucleons 2 Conserve nuclear charge (Z) If we know two of the nuclear particles, we can use these rules to identify the third particle.910Nuclear ReactionsNuclear decomposition of Radium Emission of alpha particles: 226 Ra 222 Rn + 4 He 88 86 2 Used in radiation therapyA E ZNuclear ReactionsGroup Work:What is the product of alpha particle emission by Th232? Th232 Th 90? +4 He 2Conserve A: 226 = 222 + 4 Conserve Z: 88 = 86 + 2 Loss of 2 protons and 2 neutrons11 1222Nuclear ReactionsEmission of beta particles (electrons): 131 I 131 Xe + 0 e 53 54 1 Used to diagnose thyroid disorders Conserve A: 131 = 131 + 0 Conserve Z: 53 = 54 + 1 Conversion of a neutron to a protonNuclear ReactionsGroup Work:What is the product of beta emission of Co60? Co60 Co ? + 01e 271314Nuclear ReactionsEmission of beta+ particles (positrons): 18 F 18 O + 0 e+ 9 8 +1 Conserve A: 18 = 18 + 0 Conserve Z: 9 = 8 + 1Nuclear ReactionsGroup Work:What is the product of the positron emission of Mg23? Mg23 Mg ? + 0+1e+ 12Conversion of proton to a neutron1516Nuclear ReactionsEmission of gamma rays: 224 Ra* 224 Ra + 88 88 Conserve A: 224 = 224 + 0 Conserve Z: 88 = 88 + 0 Accompanies nuclear transformations which leave excited (high energy) nuclei; no nucleon change is associated with gamma rays since A = 0 and Z = 0 for raysNuclear ReactionsEmission Reactions Emission Animation171833Group WorkIdentify the type of radiation emitted when carbon14 decays to nitrogen14. carbonnitrogenWrite a balanced equation.Types of RadiationThree types of radiation are commonly detected: alpha, beta or gamma1920Types of RadiationAlpha = 42He2+ or 42He or 42 largest, least penetrating can be stopped by aluminum foil > 103 cm, paper, skin least harmful most massive21Types of RadiationBeta = 01ehigh energy electrons (e) or positrons (e+) more penetrating stopped by 0.05  0.1 cm of aluminum travel 10 ft through air commonly emitted by TV sets electron: 01 or 01e or epositron: 0+1 or 0+1e or e+22Types of RadiationGamma = energy with no mass or charge Most penetrating radiation Stopped by 5  11 cm of aluminum or thick layer of concrete or lead Lead is commonly used to enclose radioactive materials because radiation does not penetrate readily In the 1950s, it was common to build thick concrete bomb sheltersTypes of RadiationOther particles: proton (p+ or 11p or 11H) neutron (n or 10n) neutrino (00) and antineutrino (00), which have no mass or charge and accompany emission of beta particles; these are generally ignored by chemists23244421.2 Patterns of Nuclear StabilityThe stable nuclides occur in a narrow band of N/Z values  an "island of stability". For Z = 120, N = Z 1(N/Z = 1)Eg. Ca40, O16, C12 Eg. CaOCFor Z > 20, N > Z (N/Z < 1.6)Eg. Zr90, Hg200 Eg. ZrHg25 26RadioactivityThe stable isotopes form a zigzag pattern zigwithin the island of stability. Even Z & even N: most stable Even N & even Z for 60% of the stable nuclides (157) Even N or even Z for most of the rest (102)Only 5 stable nuclides have both odd N and odd Z, one of which is nitrogen14, 147N nitrogen27RadioactivityRelative abundance of some nuclei B10 F19 Zn64 Zn19% 20% 100% 49% Zn66 28% ZnZn68 ZnB11 80%28Group WorkWhich of each pair of nuclides is most likely to be radioactive? radioactive? 16 O and 17 O 8 8 16 O and 18 O 8 8 29 Si and 28 Si 14 14 14 C and 12 C 6 6RadioactivityMagic Numbers: Nuclei with Z or N values Numbers: equal to 2, 8, 20, 28, 50, 82, 126 have been found to be particularly stable Nuclides with these numbers of protons and neutrons are especially stable (note that these are all even numbers). Super Stable Nuclides: 42He, 168O, 4020Ca293055Spontaneous Nuclear Decay ReactionsUnstable nuclides decay spontaneously to try to reach a more stable N/Z ratio, while emitting radiation at a characteristic rate. If N is too large (N/Z>1): beta particle emission is likely If Z is too large (N/Z<1): positron emission is likely We can predict nuclear decay reactions31Spontaneous DecayN to PP to N32What type of decay?N/Z = 8/6 = 1.33 Stable N/Z for light element is 1.00 decay gives smaller N/Z 14 C 14 N + 0 e6 7 1 14 N N/Z = 7/7 = 1.00 714 C 63334What type of decay?N/Z = 6/7 = 0.86 (too small) Stable N/Z for light element is 1.00 Increase ratio by positron emission or electron capture 13 N 13 C + 0 e+ 7 6 +1 13 C N/Z = 7/6 = 1.17 6 Can't get closer than this; nuclides prefer to be greater than 1 rather than less than 135What type of decay?Sometimes uses electron capture instead. Can't tell which will occur; the result is the same. 0 e + 22 Na 22 Ne 1 11 1013 N 73666What type of decay?Heavy elements decay by a combination of and decay. See the uranium series (Figure 21.4). Ultimately a heavy radioactive element will decay through a series of radioactive elements until it gets to a stable isotope of lead or bismuth. Four such series of decays are known:U Th Ac Np37Uranium SeriesPrimary mode of decay is alpha, but a few beta decays are also needed38Spontaneous DecayGroup WorkPredict the type of decay and a possible product for the following radioactive nuclides. 23290Th 2312Mg 167NN to PP to N3940Other ReactionsNuclear Bombardment: nuclei collide with Bombardment: high energy (accelerated) particles, possibly followed by decay Fission: nucleus splits into two lighter Fission: nuclei and neutrons Fusion: two light nuclei combine into a Fusion: heavier nucleus21.3 Nuclear TransmutationsBombardment reactions: Used to create new elements December 1994 in Darmstadt, Germany: 64 Ni + 209 Bi 272 ? + 1 n 28 83 111 0 Conserve A: 64 + 209 = 273 = 272 + 1 Conserve Z: 28 + 83 = 111 = 111 + 0 These reactions usually emit one or more particles, such as neutrons. This new nuclide survives for only 0.002 seconds41 4277Bombardment ReactionsReaction in a nuclear reactor 238 U +1 n 239 Np + 0 e92 0 93 1 Synthesis of transuranium elements: 238 U + 4 He 239 Pu + 31 n 92 2 94 0 238 U + 12 C 246 Cf +41 n 92 6 98 0 238 U + 14 N 247 Es + 51 n 92 7 99 0Bombardment ReactionsIn September 1982, two new elements were formed by bombardment with heavy nuclides: 58 Fe + 206 Pb 265 Hn + 1 n Hassium 26 82 108 0 58 Fe + 209 Bi 266 Mt +1 n Meitnerium 26 83 109 0 Prepared only a few atoms of each4344Group WorkWhat is the product of the following reaction?97 Mo 4221.4 Rates of Radioactive DecayNuclear decay always follows 1storder kinetics, 1stwhich gives a constant t1/2 over the course of the decay.1st Order Rate = kN (N is the # radioactive nuclei) Rate is the Activity k is the decay constant45 46+ 21H ? + 210n21.4 Rates of Radioactive DecayIntegrated Rate Law: ln(Nt/No) = kt ln(No/Nt) = +kt +kt ln(2/1) = 0.693= kt1/2Another common form of the integrated rate law: Nt = Noekt (just a different form of the 1st order ratelaw)4721.4 Rates of Radioactive Decayt1/2 = 0.693/k Nuclear decay rates are also independent of temperature. Usually we cite t1/2 instead of the rate constant.4888Decay curve for 198AuSuccessive halflives half(t1/2 ) have the same value. The radiation intensity and the number of radioactive nuclei decrease by a factor of 2 during each halfhalflife.Rates of DecayThe rate of decay, as well as the type and energy of the radiation, determines the damage caused by radiation.4950KineticsCan use kinetics, just like in Chapter 14, to do various calculations.How much nuclide is left after ___ time? How long do we have to store nuclear waste? (Usually 10 t1/2: 210 = 0.000977, so 99.9023% has decayed) 51Cr (t 1/2 = 27.8 days) is stored for > 10 months How much time has elapsed if conversion is ___% complete?HalfLivesGold198 undergoes beta decay to give Goldmercury198 with a halflife of 2.7 days. mercuryhalfWhat fraction (or %) of gold198 is left goldafter 2.7 days?after 5.4 days? after 8.1 days?Use ln(N/No) = kt and k= 0.693/t1/2 0.693/51 52HalfLivesGold198 undergoes beta decay to give Goldmercury198 with a halflife of 2.7 days. How mercuryhalflong will it take for 95% of Au198 to decay? AuGroup WorkGold198 undergoes beta decay to give Goldmercury198 with a halflife of 2.7 days. mercuryhalfWhat fraction (or percent) of gold198 is left goldafter 14 days?535499Archeological DatingRadiocarbon dating uses 14C content 14C is produced by bombardment of 14N with neutrons (in cosmic rays)14 N 7Archeological DatingWhen a plant or animal dies, it no longer incorporates new 14C, and 14C content begins to decrase, causing the 14C decrase, content to become less than that in the atmosphere Count bristlecone pine tree rings to bristledate the rings; correlate with a measurement of their 14C content (University of Arizona)55 56+ 10n 146C + 11H14C is incorporated into living systems, but undergoes radioactive decay with a halflife halfof 5730 years:14 C 6 147N + 01eArcheological DatingLiving tissue has an activity of 15.3 disintegrations per minute per gram of Carbon After 1 halflife: Activity = 7.65 dis/min gC halfdis/min After 2 halflives: Activity= 3.8 dis/min gC halfdis/min Can measure > 0.03 dis/min g 15.3 0.03 in about 9 t1/2 Thus, the effective time range is < 9 x 5730 ~ 50,000 yearsGeological DatingGeological dating is similar to archeological dating, but uses longerlived nuclides longerMeasure ratio of 40K to 40Ar in rocks 40 K + 0 e 40 Ar 89% 19 1 18 40 K 40 Ca + 0 e 11% 19 20 1 Combined halflife is 1.27 x 109 years halfMeasure ratio of 238U to 206Pb in rocks 238U ... 206Pb t1/2 = 4.5 x 109 years5758Geological DatingOldest rocks from Earth's Crust have been determined to be 3x109 yrs old.21.5 Detection of RadioactivityStudy nuclear properties by studying the radiation emitted. Detection: film badge for personal exposure GeigerMuller counter Geigerradiation causes ionization of Ar(g), which gives a pulse of electric current that is sent to a counter detects , , or 59601010Detection of Radioactive DecayGeiger Counter21.6 Energy Changes in Nuclear ReactionsChemical reactions have energy changes of 1001000 kJ/mol 100Nuclear reactions are of interest because of their large energy output The mass of an atom is less than the separate masses of the component subatomic particles  this discrepancy is called the mass defect. defect.scintillation counter ZnS or NaI fluoresces (light flash) when irradiated; light is passed through a photomultiplier tube and recorded on a counter6162Mass Defect (m)19.9924 amu Assume 2010Ne 10p+ + 10n + 10emass of p+ = 1.00728 amu mass of n = 1.00867 amu mass of e = 0.0005486 amu20 Ne 10Mass DefectMass Defect can be calculated in two ways: Mass of Isotope Mass of (#p+ + #n + #e) Mass of Nuclide Mass Mass of (#p+ + #n)Both methods will give the same result.sum of particle masses = 20.1650 amu mass defect = 20.1650 amu  19.9924 amu = 0.1726 amu63 64Mass DefectThe energy corresponding to the mass defect is called the nuclear binding energy, E. Einstein's equation is used to determine the massenergy equivalence: massE = mc2 1 amu = 1.66056 x 1027 kg c = 2.9979 x 108 m/s joule = kg m2/s265Nuclear Binding EnergyFor 2010Ne E=mc2 E = (0.1726 amu x 1.66056 x 1027 kg/amu) x kg/amu) (2.9979 x 108 m/s)2 E = 2.576 x 1011 J for one atom For 1 mole of atoms (6.022 x 1023 atoms): E = 1.551 x 1013 J/mol = 1.551x1010 kJ/mol!661111Nuclear Binding EnergyMega Electron Volts (MeV) (MeV)It is common to use MeV as a unit to get convenient numbers for single atoms: 1 MeV = 1.6602 x 1013 J E = 2.576 x 1011 J x (1 MeV/1.6602 x 1013 J) = 160.8 MeV for one Ne20 atom NeFor Ne, Binding Energy/nucleon Ne, = 160.8 MeV/20 nucleons = 8.04 BE/Nucleon67Binding Energy per Nucleonfissionfusion68Binding Energy per NucleonBinding EnergyThe curve is smooth, with spikes for very stable nuclides: 42He, 126C, 168O (N = Z = even) Maximum value at 5626Fe, which is prevalent in Earth's crust. Elements with Z = 2030 are prevalent in 20the crust, as are 16O, 12C, and 14N No elements heavier than those at the maximum in the curve are present in amounts >1% in the crust69 70fissionfusionFigure 21.13 in TextBinding EnergyLight nuclides undergo fusion or bombardment to convert to other nuclides closer to the maximum value Heavy nuclides undergo fission to give nuclides closer to the maximum value If a nuclear reaction gives products with a higher nuclear binding energy, then energy is released by the reaction. To calculate the energy released, m is products reactants: E = mc2 products71Group WorkWhich of the following nuclides might undergo nuclear fission to form more stable nuclides? 21 Ne 10 127 Te 52 237 Np 93 27 Si 14 40 Ca 20721212Energy Change for a Nuclear ReactionWhat is the energy change for the following reaction? 2H + 3H 4He + 1n 3.01605 amu 2.01410 amu 4He 4.00260 amu neutron 1.00866 amu2H73Energy Change for a Nuclear ReactionWhat is the energy change for the following reaction? 2H + 3H 4He + 1n m=(4.00260 + 1.00866)  (2.01410 + 3.01605) 3.01605) = 5.01126 amu  5.03015 amu = 0.01889 amu E = mc2 = 2.82x1012 J = 1.70x109 kJ/mol!743HGiven:21.7 Nuclear FissionSome nuclides undergo spontaneous fission; others undergo fission when bombarded with another nuclide or with a nucleon 235U is used in nuclear power plants 235 U + 1 n 236 U mixture of products 92 0 92 236 U 92 Kr + 141 Ba + 31 n + 92 36 56 0 236 U 90 Sr + 143 Xe + 31 n + 92 38 54 0 236 U 94 Zr + 140 Ce + 21 n + 92 40 58 0 and others75Nuclear FissionAverage of 1 n is consumed, but an average of 2.4 n are produced, so more reaction occurs with the new neutrons and the reaction speeds up. This is called a chain reaction. reaction.76Chain ReactionOne step in a chain reaction produces more neutrons than it consumes.Chain ReactionSuccessive steps get faster and faster ....How do we control the reaction?Chain reaction77Critical Mass781313Nuclear ReactorThe size and shape of the uranium fuel determines how many neutrons escape and how many react. If we exceed some critical mass, the reaction mass, becomes increasingly faster and results in a nuclear explosion. To control the process, we must remove some neutrons and slow down fast neutrons so they will react.79Reactor CoreWe use B or Cd control rods to absorb neutrons. 105B + 10n 73Li + 42He80Nuclear ReactorFuel is not pure 235U. Usually use U3O8 enriched from a natural 0.7% 235U to 23% 235U. 2Use a moderator to slow down neutrons: H2O or D2O or graphite. Get an energy output of 200 MeV/atom or 2 x 1010 kJ/mol as the kinetic energy of the products. Use this kinetic energy to heat water (the coolant) to 310350oC (under pressure to 310prevent boiling).Diagram of Nuclear Reactor8182Diagram of Nuclear Reactor21.8 Nuclear FusionFusion is already a source of energy; this is the process that produces sunlight. Sun: 411H 42He + 20+1+ + 25 MeV energy Need energy to initiate fusion (to overcome internuclear repulsions). In the sun, the intertemperature is about 107 K83841414Nuclear FusionIn a fusion bomb (hydrogen bomb), high temperature and pressure are provided by a fission explosion.Nuclear FusionTo date, it has been possible to carry out controlled fusion, but the input energy still exceeds the output energy. The most likely candidate for a fusion reaction is: 2 H + 3 H 4 He + 1 n 1 1 2 08586Nuclear Fusion2 H is deuterium (D), available from water 1 (heavy water) 3 H is tritium (T), available from the 1 bombardment of Li with neutrons. We currently have about a thousandyear thousandsupply of lithium.21.9 Biological Effects of RadiationCan damage tissue cells Radiation comes continuously from many sources besides nuclear power plants and applications of isotopes Natural radiation sources:granite soil water food air87brick concrete cosmic rays (airplane flights) radon in houses88Bioligical EffectsDamage from radiation depends on:Activity of radioactive substance Type of radiation Length of exposure Source: inside or outside bodyBiological Effects of RadiationAmount of radiation exposure measured in rem rad = radiation absorbed dose (102 J/kg tissue) RBE = relative biological effectivenessRBE = 1 for xray, , xRBE = 2.5 for slow neutrons RBE = 10 for , protons, fast neutrons RBE = 20 for heavy ionsWater in our bodies is ionized forming free radicals. Free radicals are highly reactive species that can cause unwanted cellular reactions.891 rem = 1 rad x 1 RBE rem = roentgen equivalent for man901515Biological Effects of RadiationSingle dose of 025 rem: no effect 025100 rem: temporary blood cell 25changes 100300 rem: radiation sickness; 100decrease in white blood cells 400600 rem: 50% chance of death 400> 1000 rem: 100% chance of deathBiological Effects of RadiationNormal exposure = 360 mrem (0.36 rem) per rem) year, which produces no observable effects9192Biological Effects of RadiationCalculate your radiation exposure:Cosmic radiation at sea level 27 mrem/year Add 1 for every 250 ft elevation 4 for Phoenix Radiation from earth 28 Building materials in houses 4 Radon gas from the ground 200 Radiation from food and water 39 Jet plane travel (9.5 mrem/hr) ___ If you smoke (~1300 mrem/yr) ___210PoBiological Effects of RadiationAverage medical exposure Add 6 for each chest xray xAdd 245 for intestinal xray xSmoke detectors Power plants 2555 mrem/yr 25____ ____ 10 1Your total exposure this year: _____ mremin cigarette smoke9394Medical Applications of IsotopesMedical diagnoses (Radiotracers) 99Tc for tumors in spleen, liver, brain, thyroidtracer put into a metabolite that concentrates in cancerous cells131I or 123I in thyroid Cancer therapy  destroy cells with rays131Ifor thyroid cancers for lung cancer 32P for eye tumors198Au95 961616...
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 Spring '08
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 Chemistry, Atom, Nuclear Chemistry

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