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NUCLEAR CHEMISTRY -the study of nuclear transformations/reactions and their uses in chemistry Definition: 1. Nuclear Reactions changes in matter originating in the nucleus of an atom 2. Radioactive Substances substances that emit radiation due to changes in the nclei 3. Atomic Number # protons 4. Mass Number # protons + # neutrons 5. Isotopes atoms with the same atomic # but different mass # (different # of neutrons) 6. Radionuclides nuclei that are radioactive 7. Radioisotopes atoms containing radionuclides Radioactivity - is the process by which atoms emit energetic particles as rays. These particles or rays are termed radiation. - is a nuclear event: matter and energy released during this process come from the nucleus.

Mass number (p+n) 19F Atomic number (p) 9

- only unstable nuclei undergo change and produce radioactivity, the process of radioactive decay; in the process, they spontaneously emit particles and/or energy. Isotopes different atoms of the same element having different masses. Isotopes and nuclide may be used interchangeably)

1H 1
Hydrogen-1 Name Symbol Alpha () ( 4He2+ , 4 He ) 2 2 Beta ( )
0 0 ( -1 e , -1 )

4 2H
Hydrogen-2 Charge +2 Mass (amu) 4.0026 Identity Helium nucleus

3 1H
Hydrogen-3 Velocity 5-10% of the speed of light up to 90% of the speed of light speed of light Penetratio n Low

and

Electron

-1

0.000549

Medium

Gamma ( ) Positron,
+

Radiant Energy
0 0 +1 or +1 e

High

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Other particles involved in artificial nuclear reaction: a. neutron, n b. proton, p

1 = 0n

c. deuteron/deuterium, d = 2H 1 d. triton/tritium t = 3H

= 1H 1

Properties of Alpha, Beta, and Gamma Radiation , , are collectively termed ionizing radiation. Ionizing radiation produces a trail of ions throughout the material that it penetrates, thus changing the chemical composition of the material. When the material is living tissue, radiation-induced illness may result. Nuclear Reactions Writing A Balanced Nuclear Equation Nuclear Equation used to represent the process of radioactive decay. show the transformation of nuclei that result from a nuclear reaction these differ from chemical equations in that the atoms present on the reactant side will not be the same as the those present on the product side. When writing a balanced equation, remember that: the total mass on each side of the reaction must be identical the sum of the atomic numbers on each side of the reaction arrow must be identical Natural Radioactivity 1. Alpha Emission consists of the ejection of an -particle; involves decrease in mass # and atomic # e.g.

210 206 4 84 Po 82 Pb + 2 He
Polonium-210 Lead-206 Helium-4

2. Beta Emission - consists of the ejection of an -particle; involves increase in atomic # e.g.

234 Th 234 Pa + 0 e 90 91 -1

3. Gamma Radiation does not cause changes in the mass number nor the atomic number of the nucleus e.g.

122 122 0 52Te 52Te + 0

4. Positron Emission consist of ejection of positive electron; involves decrease in atomic number e.g.
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122 I 122 Te + 0 e 53 52 1 +

Nuclear Transmutation/Induced Radioactivity - Bombardment Reaction - Cyclotron accelerator is commonly used a.

27 Al + 1n 13 0

radioactive decay neutron bombardment 28 Al 28 0 -------------- > ----------->14 Si + -1 e 13

Bombardment reaction 30 P + 1n -------------- > 15 0
4 2

b.

27 Al + 4 He 13 2
14 7

e.g.

N +

He

17 8

O +

1 1

H
14 7

Shorthand Notation for Transmutation:

N (,p) 17 O 8
product nucleus ejected particles bombarding/incident particle target nucleus

Ex.

75 As + 4 He Br +1 n 78 33 2 35 0

75 33

As( ,n) 78Br 35

c. Electron Capture: a process whereby a nucleus captures an orbital electron from a K/L shell (an inner shell electron).

0 197 197 -1e + 80Hg -------------- > 79 Au

Exercises:

1.

The carbon-14 isotope forms when atmospheric nitrogen is bombarded by cosmic rays.
14 7

N + 01n 14C + X 6

X =

2.

Uranium-238 has a half-life of about 4.5 billion years and is used to date very old rocks.
238 92

U 8 4 He + 2

296 82

Pb + X

X =

3. Uranium-235 undergoes fission when bombarded slow moving neutrons.

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235 92

U + 01n 36 Kr + 139 Ba + X 94 56

X =

4.

The carbon-14 isotope undergoes beta decay. This isotope has a half-life of 5730 years and is used to date once living plants and animals.

5. The potassium-40 isotope undergoes electron capture. This isotope has a half-life of about 1.2 billion years and is also used to date rocks.

Nuclear Structure and Stability Binding Energy the energy that holds the protons, neutrons, and other particles together in the nucleus. When an isotope decays, some of this binding energy is released. This released energy is the source of the high-energy radiation emitted and the basis for all nuclear technology. nuclear stability correlates with the ratio of neutrons to protons in the isotope NUCLEAR STABILITY Because protons are positively charged, protons will repel each other. protons and neutrons are held together by strong nuclear force, but nuclei with more than one proton require neutrons to separate protons from each other More protons present more neutrons needed to bind the nucleus. For elements up to atomic number 20, theres a 1:1 ratio of proton and neutrons. Above Z=20, # neutrons > # protons (see Fig. 21.2) for stable atom All nuclei with 84 or more protons are radioactive Heavier nuclei (those with mass numbers > 80) can split into smaller, more stable nuclei: nuclear fission Nuclear Stability Trends Nuclei with a large number of protons (84 or more) tend to be unstable.

naturally occurring isotopes containing 2, 8, 20, 50, 82 or 126 PROTONS and NEUTRONS are stable. (Magic Numbers) Isotopes with even numbers of protons or neutrons are generally more stable than those with odd numbers of protons or neutrons.
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All isotopes (expect hydrogen-1) with more protons than neutrons are unstable. However, the reverse is not true. Predicting type of Nuclear Reaction:

1. 2.

high n/p ratio emission is favored to lower n/p ratio ( n, p)

low n/p ratio positron emission 3. atomic # 84 tend to undergo emission to decrease # n and # p. Half-Life, t1/2 - Is the time required for one-half of a given quantity of a substance to undergo change. - Isotopes with very short half-lives decay rapidly; they are very unstable.

1 0m 0 g

oe n 0 g 2 m e . 5m 5 tc g h lf-life a h lf-life a 2 h 4 4 h to l 8 ta

Important equations (based on 1st order kinetics) 1. rate = kN = -dN/dT N amount of radioactive material k 1st order rate constant Nt amount of substance at time t No initial amount of substance t time t1/2 half-life

2. ln

Nt No

= -kt

3. k =

4. t1/2

0.693 t1/2 0.693 = k

Sample Problem. 18F is found to undergo 90% radioactive decay in 366 min. What is its computed half-life from this observation? [t1/2 = 110 min]

SOME TERMS: Chain reactions uncontrolled reaction/escalation of fission energy released Critical mass amount of fissionable material large enough to maintain a chain reaction of constant fission rate Supercritical mass excess critical mass NUCLEAR POWER 1. Nuclear Fission
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Fission splitting of heavy nuclei; occurs when a heavy nuclear particle is split into smaller nuclei by a smaller nuclear particle (such as a neutron). This splitting process is accompanied by the release of large amount of energy(exothermic). Ex. In a nuclear reactor

nuclear energy heat energy mechanical electrical nuclear reactor steam turbine electricity

The fission reaction, once initiated, is self-perpetuating. For example, neutrons are used to initiate the reaction:

1 235 236 92 146 1 0 n + 92U 92U 36Kr + 56Ba + 3 0 n + energy

Fuel Unstable Products of reaction - the process of intensification is referred to as a chain reaction. Atomic Bomb

A small atomic bomb is equivalent to 20,000 tons of TNT. A ton of TNT releases 4 x 10

9 J of energy, so an atomic bomb produces 8 x 1013 J. U-235 was used in the A-bomb dropped at Hiroshima on August 6, 1945 killing 70,000 people. Three days later, an A-bomb made of Pu-239 exploded over Nagasaki.

TNT Subcritical

U-235 neutron

Nuclear Chain Reaction

Cross-section of an atomic bomb

1n + 235U 0 92 1n + 235U 0 92 1n + 235U 0 92

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90Rb + 144Cs + 2 1n 31 55 0 87Br 5 146La + 31n + 35 57 0 72Zn + 160Sn + 4 1n 30 62 0

Nuclear Fussion Fusion - meaning to join together, results from the combination of two small nuclei to form a larger nucleus with the concurrent release of large amounts of energy. - liberates more energy than fission (also exothermic) - although fusion is capable of producing tremendous amount of energy, no commercially successful fusion plant exist in the US. - takes place only at very high temperature, they are often called thermonuclear reactions.

SUN an example of fusion reactor. Continuous fusion process furnish our solar system with light and heat.

2H + 3H 4 He + 1n + energy 1 1 2 0
Hydrogen Bond contains solid lithium deuteride (LD) packed very tightly. Its detonation occurs in two stages 1st a fission reaction is initiated triggering the following reactions:

6Li + 2H2 4He and 2H + 2H 3He + 1H 3 1 2 1 1 1 1

Radiocarbon Dating - is the estimation of the age of the objects through measurement of isotopic ratios of carbon. - based on the measurement of the relative amounts (or ratio) of 14 C and 12 C present 6 6 in an object. - Carbon-14 dating technique is limited to objects that are less than fifty thousand years old. Applications of Radioactivity Medicine used in cancer therapy, usually to eliminate any malignant cells after surgery. Cobalt-60 is most often used. Used for diagnosis; e.g. Positron Emission Topography (PET) is a technique used to study brain disorders, C-11 is used.

Iodine-131 is used as tracer in the detection of thyroid malfunction. The patient is given Na131I solution and the rate of iodine absorption is measured. Patients an either drink or is injected with technicium-99 to obtain images of organs such as heart, liver, lungs, etc. Geiger counter (instrument used to detect radiation) Chemistry
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used in chemical analysis radioactive dating

Commercial Applications smoke alarms used Americium-241 in food preservation, gamma rays are used to kill insects, larvae and parasites

Radiation damage depend on several factors: 1. The energy of the radiation The higher the energy, the more damage it can cause. Radiation doses are measured in rads (radiation absorbed dose), where 1 rad = 102 J of energy deposited per kilogram of tissue. 2. The penetrating ability of the radiation particles are stopped by the skin or paper particles can penetrate about 1 cm rays are highly penetrating, can go through a meter of metal, concrete

3. The ionizing ability of the radiation When ionizing radiation passes through living tissue free radicals: molecules with one or more unpaired electrons short-lived and highly reactive attack cell membranes and other organic compounds like DNA 4. The chemical properties of the radiation source For example,
85 36

Kr

and

90 38

Sr

are both producers.

Since Kr is chemically inert, it passes through the body quickly and does not have much time to do damage. However, Sr is chemically similar to calcium, so it can replace calcium in the bones, where it can cause leukemia and bone cancer. Some Detrimental Effects of Radiation

1.

Strontium-90, a -emitter, can replace calcium in bones.

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2.

3. 4.

Concentration of radioactive lead-210 can build up to a high level at the surface and interior of tobacco leaves which during the combustion of cigarette could be inhaled into the respiratory tract and are eventually transported to the liver, spleen, and bone marrow. This results to a higher risk of cancer development. A dosage of 50-200 roentgen radiation will decrease white blood cell counts. Radiation can cause mutations in genes which may further lead to the production of cancerous cells.

EXERCISES 1. Thorium-232 undergoes radioactive decay in a 3 step process. equation for each step. Identify Q, R and T. a. 232 Th Q + 4 H Write a balanced nuclear

90

b.

0 Q R + -1e

c.

R T + 228Th 90

2. Balance the following reaction:

235 U + 1n ______ ______ + 2 1n 92 0 0

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Write the balanced nuclear equation for the following: a.

2 C ( 25 C 42 m ,n) 4 f 96 95

b.

2 A (_,n 2 M 7 5 g )1 1 l 3 2

c.

2 9 B (d ) ___ 0 8 i ,n 3

d.

1 C(p 1 N 2 ,_) 3 6 7

e. neutron adsorption by 107 Ag

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f.

236U (_ emission) + 90 Th ( emission) ___ (-capture) ___

4. Complete the following reactions a.

23 4 26 11 Na + 2 He ______ + 12 Mg

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b.

64 0 29 Cu 1

+ ______

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