CHEM 357

CHEM 357
Nuclear Chemistry
Gershon Amenuvor
Owusu Prince (TA)
Note Four
Nuclear Chemistry: Nuclear Fission
• Nuclear Reactor
• Nuclear fission has peaceful uses
• It is used via a controlled chain reaction to generate electricity by
converting kinetic energy from the nuclear reactor to thermal
energy
• The thermal energy is then used to turn a turbine of an electric
motor
• Despite its positive use, there are regulations that controls
intentions to build a reactor for such use
• Nuclear reactors are also used for research purposes 2
• Nuclear Reactor
• A nuclear reactor has five main components:
• The Reactor Core: It housed the fuel (U-235 enriched to 3 to
5%, contained in cylinders)
➢This generates the needed heat for energy production
➢Relative naturally occurring uranium contains only about
0.7202% of U-235
➢How is U-235 enriched to 3%?
3
• Nuclear Reactor
• The Control rods: Composed of substances (usually cadmium-
113 and boron-10) that absorb neutrons
➢This regulate the power level of the reactor (how?)
113
48Cd + 10n 114
48Cd + 00ɣ
10
0n 2α
1 7 4
5B + 3Li +
4
• Nuclear Reactor
• Moderator: It surrounds the uranium cylinders
➢Its function is to slow down the neutrons so that they can
be capture efficiently by the fuel
• A good moderator must be
➢Nontoxic, cheap, should not be converted into radioactive
substances and must be fluid so that it can serve as a
coolant at same time
5
• Nuclear Reactor
• Coolant: It cools the heat to steam for use
➢Coolants are usually light or heavy water
➢Reactors that use D2O are called heavy water reactors
• Containment shell
➢This houses the entire reactor
➢The shell is reinforced to prevent leakage of radiation and
fire outbreak in case of malfunction leading to accident
6
• A schematic
diagram of a
nuclear fission
reactor
7
• Nuclear Breeder Reactors
• Breeder reactors were born from the scarcity of U-235
• Fertile isotopes such U-238 and Th-232 are used to produce
fissionable isotopes
• For a example, U-238 is transmuted to fissionable Pu-239 via
neutron capture and beta elimination
8
• U-238 Breeder Reactor
0n −1β
238 1 239 239 0
92U + 92U 93Np + t1/2 = 23.4 min.
−1β
239 239 0
93Np 94Pu + t1/2 = 2.35 days
Fissionable isotope
9
• Th-232 Breeder Reactor
0n −1β
232 1 233 233 0
90Th + 90X? 91Pa + t1/2 = 22 min.
−1β
233 233 0
91Pa 92Q? + t1/2 = 27.4 days
Fissionable isotope
10
• Is Nuclear Reactor the way forward for energy?
• There are several hazard issues associated with nuclear
reactors.
• Many fission products are dangerous radioactive substances.
• These substances and radiations will escape into the
environment during accidents.
• The radio active wastes generated must be disposed off
appropriately.
11
Nuclear Chemistry: Nuclear Fusion
• Nuclear fusion is the process by which small nuclei combine to
form larger nuclei
• Fusion reactions take place only at very high temperatures
• For this reason, fusion reactions are called thermonuclear
reactions
• Fusion reactions also produce a large amount of energy
12
• Nuclear fusion reactions occur in the sun and stars
• The sun consists of about 73% of hydrogen and 26% helium
• The temperature in the sun is large enough to cause the
following reactions: 1
+1β
1 2 0
1H + 1H 1H + 1
1 2 3
1H + 1H 2He 2
3
2He + 32He 4
2He + 2 11H 3
+ 32He +1β
1 4 0
1H 2He + 4
13
• Nuclear fusion is a promising energy source due to its
exothermic nature
• However, it requires a very high temperature
• One advantage of nuclear fusion over nuclear fission is that it
eliminates production of nuclear wastes
14
Nuclear Chemistry
• Group assignment (in a form of Power Point Presentation)
• Discuss:
1. The various methods of detection and measuring of
radiations (alpha, beta and gamma)
2. How is U-235 enriched to 3%
3. The difficulty in commercialising nuclear fusion reaction for
energy (using hydrogen atoms as nuclei feedstock)
15
Nuclear Chemistry: Dating Using Radioactivity
• How do archaeologists predict the ages of fossil and
artifacts, ancient towns which have been abandoned etc.?
• The ages of certain objects like animal remains and rocks
are calculated using the kinetics of radioactive nuclei.
• Once the half-life of a radioactive isotope is known, the
amount of that isotope remaining during its measurement
serves as an atomic clock in determining the age of the
object.
16
• Carbon-14 Dating
• Carbon-14 decay is used to determine the approximate ages
of fossil materials.
• Carbon-14 is produced by bombardment of atmospheric
nitrogen with neutron from cosmic rays according to the
nuclear equation:
14 1 14 1
7N + 0n 6C + 1H
• Carbon-14 decays according to the nuclear equation:
−1β
14 14 0
6C 7N + t1/2 = 5,730 yr 17
• The rate of formation of carbon-14 is nearly the same as the
rate of its disintegration.
• That is, formation of carbon-14 and its disintegration are in
chemical equilibrium.
➢Thus, concentration of carbon-14 in the atmosphere remains
constant.
14
• Carbon-14 goes on to form CO2 which is utilised by plants
and finally consumed by animals.
• Thus, every animal contains carbon-14.
18
• As long as a plant or animal lives the ratio of carbon-14 to
carbon-12 in the molecules of the plant remains the same.
• The ratio begins to change in favour of carbon-12 as soon as
the plant or animal dies.
• If the ratio of carbon-14 to carbon-12 in the remains of the
Trojan Horse decreased by half of that found in living trees,
then we can say that it has been about 5,730 years since the
tree was cut to curve the Trojan Horse.
19
𝑁0 1 𝑁0
• Recall that ln = λt; t = ln
𝑁𝑡 λ 𝑁𝑡
• Because rate is directly proportional to the amount of carbon-
14 nuclei present, we rewrite the above equation as
1 𝑁0 1 decay rate at t = 0
t = ln = ln
λ 𝑁𝑡 λ decay rate at t = t
1 decay rate of fresh sample
= ln
λ decay rate of old sample
• In fresh samples the 14C:12C ratio is abut 1:1012
20
• TRIAL QUESTIONS
• A living tree has a carbon-14 decay rate of 6.1 counts per
minutes per gram. An old walking stick curved from the same
type of tree has a decay rate of 5.2 counts per minutes per
gram. Estimate the age (in years) of the walking stick.
21
• TRIAL QUESTIONS
• The ratio of carbon-14 to carbon-12 in the atmosphere is 1.5
x 10-2 atoms of carbon-14 to one atom of carbon-12. If the
half-life of carbon-14 is 5,730 years and the ratio of carbon-
14 to carbon-12 in a fossil is 6.61 x 10-5 atoms of carbon-14
to one atom of carbon-12, calculate the age of the fossil.
22
• The drawback of Carbon-14 dating
• Dendrochronological data has shown that carbon-12 to
carbon-14 ratio in the atmosphere has changed significantly
over the ages.
• This results in a significant error in carbon-14 dating.
• Thus, correction factors have been incorporated into
radiocarbon dating
23
• Potassium-40 or potassium-Argon Dating
• Potassium-40 is radioactive, which decays in three modes:
➢Beta emission (in about 89.28%)
➢ Electron capture (in about 10.72%)
➢Positron emission (in about 0.001%)
• Potassium-40 has a very long half-life of around 1.25 billion

years.
24
• Geochemists and geologists use electron capture by
potassium-40 isotope to predict the age of rocks
40 0 40
19 K + −1e 18Ar t1/2 = 1.25 x 109 yr
• Potassium-40 decays in rock mineral to produce argon-40
• Argon-40 is trapped in the mineral until the mineral is melted
• Argon-40 released after melting the mineral is analysed by
mass spectrometer
25
• Knowing the half-life of potassium-40 isotope and the ratio of
potassium-40 to argon-40 the ages of rocks up to billion
years can be established
• This is very interesting !!!
26
• Uranium-238 Dating
• Geologists and geochemists use uranium-238 to estimate
the age of rocks, the earth and extra-terrestrial objects.
• Recall that uranium-238 decay series produces lead-206 as
the stable isotope.
• Assuming that before the volcanic eruption there was no
lead-206 present.
• If after years of existence lead-206 was found, then it
originated from uranium-238.
27
Nuclear Chemistry: Uranium-238 Decay Series
4.51 x 109 yr 24.1 day 1.17 min

➢ The times
indicate 2.47 x 105 yr
half-lives
3.82 day 1.60 x 103 yr 7.5 x 104 yr
3.05 min
26.8 min 19.7 min 1.6 x 10-4 s
20.4 yr
140 day 5 day

28
• Uranium-238 Dating
• The half-life of uranium-238 decay to thorium-234 is so large
as compared to the half-lives of all intermediates formed in
getting the sable lead-206.
• Thus, all other half-lives are considered to be negligible.
• To estimate the age of a rock, the half-life of uranium-238
decay to thorium-234 (4.51 x 109 yr) is used.
29
• Exercise: Analysis of a rock sample showed the ratio of Pb-206
atoms to U-238 atoms to be 0.215. Assuming that no lead was
originally present, that all the Pb-206 formed over the years has
remained in the rock, and that the number of nuclides in the
intermediate stages of decay between U-238 and Pb-206 is
negligible, calculate the age of the rock. The half-life of uranium-
238 decay to lead-206 is approximately 4.51 x 109 yr.
.........................................................................................................
.........................................................................................................
.........................................................................................................
.........................................................................................................
.........................................................................................................
.........................................................................................................
.................................................................................................. 13
Uses of Isotopes in Synthetic Chemistry
• Study of Reaction Mechanisms
• Sometimes, the mechanisms of chemical reactions are very
difficult to study
• This becomes extremely difficult when the incoming group
has atoms that are already existing on the parent molecule
• Take, for instance, the reaction scheme shown below; how
will you know which CO is which in the final compound?
31
• With isotopic labelling the position of the added CO can be
identified
• The carbon atom in the incoming CO can be made to be 13C
and its position in the resulting compound will be identified
• You will find the details of this in CHEM 352
32
• Consider an esterification reaction (reaction of a carboxylic
acid with an alcohol)
• This reaction produces an ester and water as a by-product
• Where is the oxygen in the water coming? How would you
know?
• Isotopic 18O labelling experiment is used to determine the
source of oxygen in the water
33

CHEM 357 - 24 - Lecture 5-6

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

CHEM 357 - 24 - Lecture 5-6

Uploaded by

Copyright:

Available Formats

• Carbon-14 decays according to the nuclear equation:

• In fresh samples the 14C:12C ratio is abut 1:1012

• Potassium-40 has a very long half-life of around 1.25 billion

4.51 x 109 yr 24.1 day 1.17 min

26.8 min 19.7 min 1.6 x 10-4 s

140 day 5 day

You might also like