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Chapter

Nuclear Chemistry
Chemistry 4th Edition McMurry/Fay
Dr. Paul Charlesworth
Michigan Technological University

Nuclear Reactions

01

Prentice Hall 2004

Chapter 22

Slide 2

Nuclear Reactions

01

4 He2+ that Alpha () Radiation: Are helium nuclei, 2

contain two protons and two neutrons.

Alpha () emission reduces the mass number by 4 and the atomic number by 2.

Prentice Hall 2004

Chapter 22

Slide 3

Nuclear Reactions

02

Beta () Radiation is an electron. It carries a negative charge, and negligible mass. Beta emission () occurs when a neutron decays into a proton. The product has the same mass number, but the atomic number increases by 1. Gamma Radiation is high-energy electromagnetic radiation ( = 1011 to 1014 m). It has no charge or mass.
Chapter 22 Slide 4

Prentice Hall 2004

Nuclear Reactions

03

Positron Emission: Conversion of a proton to a neutron plus an ejected positron (+). The mass number is unchanged, but the atomic number decreases by 1. Electron Capture: Nucleus captures an inner-shell electron and converts a proton into a neutron. The mass number is unchanged, but the atomic number drops by 1.
Chapter 22 Slide 5

Prentice Hall 2004

Nuclear Reactions

05

Nucleons are subatomic particles in the nucleus. The mass number (p+ + n0) and the atomic number (p+) are obtained from the nucleons.

Prentice Hall 2004

Chapter 22

Slide 6

Nuclear Reactions

06

Write balanced equations for:


1. Alpha emission from curium-242 2. Beta emission from magnesium-28 3. Positron emission from xenon-118 4. Electron capture by polonium-204

What particle is produced by decay of thorium-214 to radium-210?


Chapter 22 Slide 7

Prentice Hall 2004

Radioactive Decay Rates

01

Prentice Hall 2004

Chapter 22

Slide 8

Radioactive Decay Rates

01

Radioactive decay is kinetically a first-order process.

Decay Rate = k x N

The integrated form of the first-order rate law is:

Nt = kt ln N0
Prentice Hall 2004 Chapter 22 Slide 9

Radioactive Decay Rates

02

Half-Life: Radioactive decay is characterized by a half-life, t1/2, the time required for the number of radioactive nuclei in a sample to drop to half its initial value.

ln 2 t1 = k 2
Prentice Hall 2004 Chapter 22 Slide 10

Radioactive Decay Rates

03

Prentice Hall 2004

Chapter 22

Slide 11

Radioactive Decay Rates

04

The decay constant for sodium-24, a radioisotope used medically in blood studies, is 4.63 x 102 h1. What is the half-life of 24Na?

The half-life of radon-222, a radioactive gas of concern as a health hazard in some homes, is 3.823 days. What is the decay constant of 222Rn?

Prentice Hall 2004

Chapter 22

Slide 12

Carbon Dating

01

Carbon-14 is produced in the upper atmosphere by the bombardment of nitrogen atoms with neutrons: 14 N + 1 n 14 C + 1 H 7 0 6 1 Radioactive 14CO2 is produced, which mixes with ordinary 12CO2 and is taken up by plants during photosynthesis.
Prentice Hall 2004 Chapter 22 Slide 13

Carbon Dating

02

During an organisms life, 14CO2 and 12CO2 are in a dynamic equilibrium at a ratio of 1 part in 1012. When an organism dies, the 14C/12C ratio decreases as 14C undergoes decay to 14N. Measuring the 14C/12C ratio determines the age of the sample with a high degree of certainty. Ages of 100020,000 years are commonly determined. The half-life for 14C is 5730 years.
Prentice Hall 2004 Chapter 22 Slide 14

Carbon Dating

04

The carbon-14 decay rate of a sample obtained from a young live tree is 0.260 disintegrations s1 g1. Another sample prepared from an archaeological excavation gives a decay rate of 0.186 disintegrations s1 g1. What is the age of the object?
Prentice Hall 2004 Chapter 22 Slide 15

Nuclear Stability

01

Stable refers to isotopes whose half-lives can be measured. Those which decay too fast to be measured are called unstable. Isotopes that do not undergo radioactive decay are called nonradioactive or stable indefinitely.
Chapter 22 Slide 16

Prentice Hall 2004

Nuclear Stability

02

The band of nuclear stability indicates neutron and proton combinations giving rise to observable nuclei with measured halflives. The island of stability corresponds to predicted super heavy nuclei first observed in 1999.
Chapter 22 Slide 17

Prentice Hall 2004

Nuclear Stability

03

Every element has at least one radioactive isotope. Ratio of n0 to P+ increases for elements heavier than calcium. All isotopes heavier than bismuth-209 are radioactive. Chart shows odd/even ratio of protons to neutrons for nonradioactive isotopes.
Chapter 22 Slide 18

Prentice Hall 2004

Nuclear Stability

04

Nuclei with higher neutron/proton ratios tend to emit beta particles. Nuclei with lower neutron/proton ratios tend to favor positron emission, electron capture, or alpha emission.
Chapter 22 Slide 19

Prentice Hall 2004

Nuclear Stability

05

Radioactive products of a radioactive decay will undergo further disintegration. Some nuclei undergo a whole series of disintegrations called a decay series, leading to nonradioactive species.
Chapter 22 Slide 20

Prentice Hall 2004

Energy Changes

01

Since neutrons act as glue by overcoming protonproton repulsions, the strength of these forces should be measurable. However, the activation energy required to force elementary particles close enough for reaction is very high and requires temperatures of about 107 K. Using Einsteins equation E = mc2, we can attempt to calculate energies.
Chapter 22 Slide 21

Prentice Hall 2004

Energy Changes

02

Consider the formation of a helium-4 nucleus:


Total theoretical mass of 2n + 2p = 4.031 88 amu Observed mass of helium-4 nucleus = 4.001 50 amu Mass difference = 0.030 38 amu

Mass difference is called the mass defect of the nucleus. It results from combination of protons and neutrons. It is converted to energy during reaction and is a direct measure of nucleon binding energy.
Chapter 22 Slide 22

Prentice Hall 2004

Energy Changes

03

Using the Einstein equation, we can calculate the binding energy for a helium-4 nucleus:

The mass defect = 0.030 38 amu = 0.030 38 g/mol = 3.038 x 105 kg/mol. E = mc2 = 2.73 x 109 kJ/mol.

The binding energy for helium-4 nucleus is 2.73 x 109 kJ/mol. Which means that 2.73 x 109 kJ/mol is released when helium-4 nucleus formed.
Chapter 22 Slide 23

Prentice Hall 2004

Energy Changes

04

Binding Energies are usually expressed on a per nucleon basis using the electron volt (eV) as the energy unit. 1 eV = 1.60 x 1019 J and 1 MeV = 1.60 x 1013 J. Helium-4 binding energy:
2.73 1012 J/mol 1 nucleus 1MeV He 4 binding Energy = 6.022 10 23 nuclei/mol 13 J 4 nucleons 1.60 10 He 4 binding Energy = 7.08 MeV/nucleon

Prentice Hall 2004

Chapter 22

Slide 24

Energy Changes

05

Prentice Hall 2004

Chapter 22

Slide 25

Energy Changes

06

Helium-6 is a radioactive isotope with t1/2 = 0.861 s. Calculate the mass defect (in g/mol) for the formation of a 6He nucleus, and calculate the binding energy in MeV/nucleon. Is a 6He nucleus more stable or less stable than a 4He nucleus? (The mass of a 6He atom is 6.018 89 amu including electrons.)

Prentice Hall 2004

Chapter 22

Slide 26

Nuclear Fission and Fusion

01

Nuclear Fission is the fragmentation of heavy nuclei to form lighter, more stable ones.

Prentice Hall 2004

Chapter 22

Slide 27

Nuclear Fission and Fusion

02

Nuclear Fission is the fragmentation of heavy nuclei to form lighter, more stable ones. Neutrons released in the fission of 235U can induce three more fissions, then nine, and so on leading to a chain reaction. Critical mass is the mass required for the chain reaction to become self-sustaining.
Chapter 22 Slide 28

Prentice Hall 2004

Nuclear Fission and Fusion

03

How much energy (in kJ/mol) is released by the fission of uranium-235 to form barium-142 and krypton-91? The fragment masses are 235U (235.0439 amu),
142Ba

(141.9164 amu), 91Kr (90.9234 amu), and


A = 1.68 x 1010 kJ
Chapter 22 Slide 29

n (1.00866 amu).
Prentice Hall 2004

Nuclear Fission and Fusion

04

Nuclear Fusion is the formation of heavier nuclei by the joining of lighter ones. Fusion products are generally not radioactive. Fusion requires high energies (temperatures over 107 K) to overcome the nuclear repulsions. The highest energies obtained in a tokamak are about 3,000,000 K, but this still hasnt been enough. Fusion reactions are also called thermonuclear.

Prentice Hall 2004

Chapter 22

Slide 30

Nuclear Fission and Fusion

05

Nuclear Reactors control the fission of 235U and use the energy produced to heat water that drives steam turbines.

Prentice Hall 2004

Chapter 22

Slide 31

Nuclear Transmutation

01

Nuclear Transmutation is the change of one element into another. Achieved by bombarding atoms with high-energy particles in a particle accelerator. Transmutation can synthesize new elements.
Chapter 22 Slide 32

Prentice Hall 2004

Nuclear Transmutation

02

Cyclotrons consist of D-shaped electrodes (dees) with a large, circular magnet above and below the vacuum chamber. Particles are accelerated by making the dees alternatively positive and negative. When the particles are moving at sufficient velocity they are allowed to escape the cyclotron and strike the target.
Chapter 22 Slide 33

Prentice Hall 2004

Detecting Radioactivity

01

Matter is ionized by radiation. We can detect radiation by measuring its ionizing properties. Ionizing radiation includes particles, particles, rays, X rays, and cosmic rays. ray & X rays are high-energy photons ( = 108 to 1011 m). Cosmic rays originate in interstellar space.
Chapter 22 Slide 34

Prentice Hall 2004

Detecting Radioactivity

02

A Geiger counter determines the amount of ionization by detecting an electric current. A thin window is penetrated by the radiation and causes the ionization of Ar gas. The ionized gas carried a charge and so current is produced. The current pulse generated when the radiation enters is amplified and counted.
Chapter 22 Slide 35

Prentice Hall 2004

Detecting Radioactivity

04

Scintillation counters use a substance called phosphor (sodium iodide & thallium iodide), which emits a flash of light when struck by radiation. Flashes can be counted electronically and converted to an electric signal. Radiation intensity is expressed in different ways. Some measure decay events, others measure exposure or biological consequences.
Chapter 22 Slide 36

Prentice Hall 2004

Detecting Radioactivity

05

Radiotracers (radio-labels) are used to follow an element through a chemical reaction. Photosynthesis has been studied using 14Ccontaining carbon dioxide: sunlight 14 14 6 CO2 + 6H2O C6H12O6 + 6O2 chlorophyll The carbon dioxide is said to be 14C-labeled.
Chapter 22 Slide 37

Prentice Hall 2004

Biological Effects of Radiation

01

The penetrating power of radiation is a function of its mass: -rays > -particles >> -particles. When ionizing radiation passes through tissue it removes an electron from water to form H2O+ ions. The H2O+ ions react with another water molecule to produce H3O+ and a highly reactive OH radical. Free radicals generally undergo chain reactions, producing many radicals in the biomolecules.
Chapter 22 Slide 38

Prentice Hall 2004

Biological Effects of Radiation

02

-rays are particularly harmful


because they penetrate in the same way as X rays.

-particles interact with the skin and -particles interact


up to 1 cm into the tissue

-particles are particularly


dangerous when ingested or inhaled.

Prentice Hall 2004

Chapter 22

Slide 39

Biological Effects of Radiation

03

Prentice Hall 2004

Chapter 22

Slide 40

Biological Effects of Radiation

06

Not all forms of radiation have the same efficiency for biological damage. To correct, the radiation dose is multiplied by the relative biological effectiveness (RBE), which gives the roentgen equivalent for man (rem). RBE is about 1 for - and - and 10 for radiation. SI unit for effective dosage is the Sievert (1 Sv = RBE x 1 Gy = 100 rem).
Chapter 22 Slide 41

Prentice Hall 2004

Biological Effects of Radiation

07

Prentice Hall 2004

Chapter 22

Slide 42

Biological Effects of Radiation

08

Prentice Hall 2004

Chapter 22

Slide 43