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Chapter 11

Nuclear Chemistry

The phenomenon of radioactivity was discovered


by Henri Becquerel in 1896. Becquerel noted that
photographic plates had bright spots when they
were exposed to uranium minerals. This radiation
was found to be composed of three types when
exposed to an electric field.

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We write nuclear equations using nuclide symbols. Nuclear


equations are balanced when the total mass number and the
atomic number on both reactant and product sides are equal.
Lets look at the decay of uranium-238.

Radioactive decay is the process in which a


nucleus spontaneously disintegrates, giving off
radiation.
A nuclear bombardment reaction is a nuclear
reaction in which a nucleus is bombarded, or
struck, by another nucleus or by a nuclear particle.

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Symbols for other particles are given below:

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Proton

1
1

H or 11P

Neutron

1
0

Electron

0
-1

Positron

0
1

Gamma photon

0
0

n
e or -01

e or 01

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A beta particle is an electron. Beta emission


occurs when a nucleus decays by emitting a beta
particle, an electron.

From the periodic table, we can see that the atomic


number of radon is 86 and the atomic number of
polonium is 84. For the alpha particle symbol, both
He and are correct.
222
86

A positron is similar to an electron, but has a


positive charge. Positron emission occurs when a
nucleus decays by emitting a positron.
A gamma photon is a particle of electromagnetic
radiation that has higher energy and a smaller
wavelength than an x-ray.
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222
86

218
84

Rn 42 He +

Po

218
84

Po

To check, total the mass numbers and atomic


numbers on each side of the reaction.
Mass numbers:
222 = 4 + 218
Atomic numbers:
86 = 2 + 84
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Iodine-131 is used in the diagnosis and treatment of thyroid cancer. This isotope decays by
beta emission. What is the product nucleus?

Radon-222 is a radioactive noble gas


that is sometimes present as an air
pollutant in homes built over soil with
high uranium content (uranium-238
decays to radium-226, which in turn
decays to radon-222). A radon-222
nucleus decays to polonium-218 by
emitting an alpha particle. Write the
nuclear equation for this decay
process.

From the periodic table, we find that the atomic number of iodine is 53.
The beta particle symbol is correct as either e or .
131
53

I -01e + AZ X

131
53

I -01 + AZ X

Now find the atomic and mass number of the


product:
131 = 0 + A
53 = 1 + Z
A = 131
Z = 54
Next, use the atomic number to find the symbol: Xe.
131
53

I -01e +

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Rn 42 +

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131
54

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Xe

131
53

I -01 +

131
54

Xe
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Nuclear Stability
It is reasonable to wonder how a nucleus with
positively charged protons is held together, given
that positively charged particles repel each other.
The stability of the nucleus is due to the strong
nuclear force. The nuclear force acts only at very
short distances, about 10-13 m. At this distance it is
stronger than the electric repulsion.

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The shell model of the nucleus is a nuclear model in


which protons and neutrons exist in levels, or shells,
analogous to the shell structure that exists for electrons.
Just as certain very stable numbers of electrons (2, 10,
28, and so on) occur when a shell is filled, so there are
magic numbers for nucleons.
A magic number is the number of nuclear particles in a
completed shell of protons and neutrons.
For protons, the magic numbers are 2, 8, 20, 28, 50,
and 82. For neutrons, the magic numbers also include
114.
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A plot of number of protons


versus number of neutrons
for each stable nuclide
yields a band of stability,
the region in which stable
nuclides lie.
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For stable nuclides with Z 20, the ratio of


neutrons to protons is between 1 and 1.1.
For stable nuclides with Z > 20, the ratio of
neutrons to protons increases to about 1.5. This is
believed to be due to the increasing repulsion
between protons, which requires more neutrons to
increase the strong nuclear force.
No stable nuclide exists for Z > 83, perhaps
because the proton repulsion becomes too great.
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Predict which nucleus in each pair should be more stable and explain why.

3.

a. Astatine-210 has 85 protons and 125 neutrons.


Lead-207 has 82 protons and 125 neutrons.
Lead-207 is more stable because it has a magic number
of protons. Also, At has > 83 protons.

Positron emission
Emission of a positron particle from an
unstable nucleus. Positron emission is
equivalent to a proton converting to a neutron.

b. Molybdenum-91 has 42 protons and 49 neutrons.


Molybdenum-92 has 42 protons and 50 neutrons.
Molybdenum-92 is more stable because it has a magic
number of neutrons.
c.

Calcium-37 has 20 protons and 17 neutrons.


Calcium-42 has 20 protons and 22 neutrons.
Calcium-42 is more stable because it has an even number of neutrons. (Both
have a magic number of protons.)

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There are six common types of radioactive decay.


1.

4.

Alpha emission
Emission of an alpha particle from an unstable
nucleus.

2.

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Electron capture
The decay of an unstable nucleus by capture
of an electron from an inner orbital of the
atom. Electron capture is equivalent to a
proton converting to a neutron.

Beta emission
Emission of a beta particle from an unstable nucleus. Beta
emission is equivalent to a neutron converting to a proton.

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5.

Gamma emission
Emission from an excited nucleus of a gamma
photon, corresponding to radiation with a
wavelength of approximately 10-12 m.
Technetium-99m is an example of a
metastable nucleus; it is in an excited state
and has a lifetime of 10-9 s.

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6.

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Spontaneous fission
The spontaneous decay of an unstable
nucleus in which a heavy nucleus of mass
number greater than 89 splits into lighter
nuclei and energy is released.

Nuclides to the left of the band of stability have a neutron-toproton ratio, N/Z, that is too large. They decay by beta emission,
which reduces the N/Z ratio by converting a neutron to a proton.
Nuclides to the right of the band of stability have an N/Z ratio that
is too small. These nuclides decay by either positron emission or
electron capture. Either process increases the N/Z ratio by
converting a proton to a neutron.

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Thallium-201 is a radioactive isotope


used in the diagnosis of circulatory
impairment and heart disease. How do
you expect it to decay?

Thallium-201 has 81 protons and 120 neutrons.


N/Z < 1.5 (too small).
Thallium-201 will decay by either electron capture or
positron emissionprobably electron capture, given
that it is a heavy element.
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Radioactive Decay Series


A sequence in which one radioactive nucleus decays to a second,
which then decays to a third, and so forth, until a stable nucleus of
lead is formed.
Three radioactive
decay series are
found naturally:
uranium-238,
uranium-235,
and thorium-232.

a.
b.
c.

Yes, isotopes have similar chemical properties.


No, the hydrogen-3 water has more mass than the hydrogen-1 water.
The hydrogen-3 (tritium) water should be radioactive.

1. Nuclear Bombardment Reactions


2. Nuclear bombardment reactions are not spontaneous. They
involve the collision of a nucleus with another particle.
3. Transmutation is the change of one element into another by
bombarding the nucleus of the element with nuclear particles
or nuclei.
1. When Rutherford allowed alpha particles to collide with
nitrogen nuclei, he found that a proton was ejected and oxygen
was formed.

The radioactive decay series for uranium-238 ends with lead-206


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You have two samples of water, each


made up of different isotopes of
hydrogen: one contains hydrogen-1 and
the other contains hydrogen-3.
a. Would you expect these two water
samples to be chemically similar?

b. Would you expect these two water


samples to be physically the same?

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Sodium-22 is made by the


bombardment of magnesium-24 (the
most abundant isotope of magnesium)
with deuterons. An alpha particle is the
other product. Write the abbreviated
notation for the nuclear reaction.
Reaction :

c. Which one of these water samples would


you expect to be radioactive?
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24
12

Mg + 21H

Abbreviate d notation :
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24
12

22
11

Na + 42 He

Mg(d, )22
11Na
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A neutron is produced when lithium-7 is bombarded


with a proton. What product nucleus is obtained in this
reaction?

Radiation Counters
There are two types of devices: ionization counters and
scintillation counters.

Reaction : 73 Li + 11H 74 Be + 01n

The product is 74 Be.


When heavy nuclei are bombarded, the bombarding particles
are scattered or deflected. To produce transmutation, the
bombarding particles must be accelerated.
A particle accelerator is a device used to accelerate
electrons, protons, alpha particles, and other ions to very high
speeds.
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Radiations and Matter


Radiation from nuclear processes affects matter in
part by dissipating energy in it.

The Geiger counter is an ionization counter used to count particles emitted


by radioactive nuclei. It consists of a metal tube filled with gas, such as
argon.

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A scintillation counter detects nuclear radiation based on flashes


of light generated in a material by the radiation. A phosphor is a
substance that emits flashes of light when struck by radiation. In
the scintillation counter, the flashes of light are detected by a
photomultiplier tube.

The dissipation can ionize atoms and molecules


and, in some cases, excite electrons in matter.
When these electrons undergo transitions to their
ground states, light is emitted.
Because nuclear radiations can form ions and
break chemical bonds, they adversely affect
biological organisms.
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The activity of a radioactive source is the number of nuclear


disintegrations per unit time occurring in a radioactive material.
The curie (Ci) is a unit of activity equal to 3.700 1010
disintegrations per second.
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Biological Effects and Radiation Dosage

Rate of Radioactive Decay

The rad (from radiation affected dose) is the dosage of radiation


that deposits 1 10-2 J of energy per kilogram of tissue.

The rate of radioactive decay is the number of nuclei


disintegrating per unit time. It is proportional to the number of
nuclei in the sample.
Rate = kNt
Nt = the number of radioactive nuclei at time, t.
k = the radioactive decay constant or rate constant for
radioactive decay; it is characteristic of the nuclide.

The rem is a unit of radiation dosage that is used to relate various


kinds of radiation in terms of biological destruction. It equals the
rad times a factor for the type of radiation, called the relative
biological effectiveness (RBE).
rem = rad RBE
Beta and gamma radiation have an RBE of about 1, neutron
radiation has an RBE of about 5, and alpha radiation has an RBE
of about 10.

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The effect of radiation on a person depends on the dosage and the length of
time of the exposure. A series of small doses have less overall effect than a
large dose given all at once.
A single dose of 500 rems is fatal to most people. Detectable effects are seen
at dosages as low as 30 rems. Background radiation averages about 0.1 rem
per year but varies dramatically by location.
If you are internally exposed to 10 rads of , , and radiation, which
form of radiation will cause the greatest damage?

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First, we find the number of nuclei of thorium-234.

Nt = 50.0 10 -6 g

1 mol
6.022 10 23 nuclei

232.04 g
1 mol

Nt = 1.298 1017 nuclei


Next, we convert the activity from curies to
disintegrations per second.

The radiation has the highest RBE, so it will


cause the greatest damage.

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The thorium-234 isotope decays by emitting a beta


particle. A 50.0-g sample of thorium-234 has an
activity of 1.16 Ci. What is the decay constant for
thorium-234?

disintegra tions
s
Rate = 1.16 Ci
1 Ci
disintegra tions
Rate = 4.292 1010
s
3.700 x 1010

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Finally, we use the rate equation, understanding that 1


disintegration = 1 nuclei.

k=

rate
Nt

disintegrations
s
17
1.298 10 nuclei

4.292 1010
k=

k = 3.31 10 -7 /s
Half-life is the time it takes for one-half of the nuclei in a sample to decay.
Half-life is related to the decay constant by the following equation:

t1 =
2

0.693
k

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After one half-life, half of the sample (0.5) remains.


After two half-lives, one-fourth of the sample (0.25)
remains.

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Thallium-201 is used in the diagnosis of heart disease. This


isotope decays by electron capture; the decay constant is 2.63
10-6/s. What is the half-life of thallium-201 in days?

After three half-lives, one-eighth of the sample


remains.
This relationship is summarized in the following
equation and in the graph on the next slide.

t1
2

0.693
k

0.693
2
2.63 10 -6
s
1 min
1h
1 day
= 2.63 10 5 s

60 s 60 min 24 h

t1 =

1
Fraction remaining = ,
2
where n = number of half - lives

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t1 =

t 1 = 3.05 days
2

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The rate constant is related to the fraction of nuclei


remaining by the following equation:

N
ln t = - kt
N0
N0 is the original number of nuclei.
Nt
is the fraction of nuclei remaining at time t.
N0

Nt = 4.745 x 1015 nuclei

54.8% of nuclei remain.


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A 0.500-g sample of iodine-131 is obtained by a hospital.


How much will remain after a period of one week? The
half-life of this isotope is 8.07 days.
First, we find the value of k.

k=

N
ln t = - kt
N0
N
0.601
ln t = 1 week
week
N0
N
ln t = - 0.601
N0
Nt

= 0.548
N0

Nt is the number of nuclei at time t .

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Next, we find the fraction of nuclei remaining.

0.693
t1
2

0.693
1 week
8.07 days
7 day
0.601
k=
week

k=

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Radioactive Dating
Because the rate of radioactive decay is constant, this rate can
serve as a sort of clock for dating objects.
Carbon-14 is part of all living material. While a plant or animal is
living, the fraction of carbon-14 in it remains constant due to
exchange with the atmosphere. Once dead, the fraction of carbon14 and, therefore, the rate of decay decrease. In this way, the
fraction of carbon-14 present in the remains becomes a clock
measuring the time since the plants or animals death.
The half-life of carbon-14 is 5730 years. Living organisms have a
carbon-14 decay rate of 15.3 disintegrations per minute per gram
of total carbon.
The ratio of disintegrations at time t to time 0 is equal to the ratio
of nuclei at time t to time 0.

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A sample of wheat recovered from a


cave was analyzed and gave 12.8
disintegrations of carbon-14 per minute
per gram of carbon. What is the age of
the grain?
Carbon from living material decays at a
rate of 15.3 disintegrations per minute
per gram of carbon. The half-life of
carbon-14 is 5730 years.

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Applications of Radioisotopes: Medical Therapy and Diagnosis


Radioisotopes are used for diagnosis of many medical conditions. For example, they are used to
develop images of internal body organs so those organs functioning can be examined. More than
100 different radioactive isotopes have been used in medicine.
Radioimmunoassay is a technique for analyzing blood and other body fluids for the
presence of very small quantities of biologically active substances.
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Energy of Nuclear Reactions

Ratet = 12.8 disintegrations/min/g


Rate0 = 15.3 disintegrations/min/g
t1/2 = 5730 y

Nuclear reactions involve changes of energy on a much larger


scale than occur in chemical reactions. This energy is used in
nuclear power reactors and to provide the energy for nuclear
weapons.

Nt ratet 12.8 disintegra tions/min/ g

=
=
= 0.8366
N0 rate 0 15.3 disintegra tions/min/ g
N
N
ln t
ln t
N
N0 = ln (0.8366 )
t= 0 =
0.693
t1
0.693

2
k
5730 y
t = 1.48 10 3 y
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Applications of Radioisotopes: Chemical Analysis


A radioactive tracer is a very small amount of radioactive isotope
that is added to a chemical, biological, or physical system so as to
study the system.
Another example of the use of radioactive tracers is in isotope
dilution, a technique to determine the quantity of a substance in a
mixture or in the total volume of solution by adding a known
amount of isotope to it.
Neutron activation analysis is an analysis of elements in a
sample based on the conversion of stable isotopes to radioactive
isotopes by bombarding a sample with neutrons.

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MassEnergy Calculations
When nuclei decay, they form products of lower energy. The
change of energy is related to changes of mass, according to the
equation derived by Einstein, E = mc2.

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Nuclear fission is a nuclear reaction in which a heavy nucleus


splits into lighter nuclei and releases energy.
In other cases, a nucleus undergoes fission after being
bombarded by neutrons.
When bombarded by a neutron, uranium-238 gives three
142
90
1
possible sets of products.
54

1
0

n+

235
92

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Xe +

38

Nuclear fusion is a nuclear reaction in which light nuclei


combine to give a more stable, heavier nucleus plus possibly
several neutrons. This process releases energy.
2
1

H + 31H 42 He + 01n

Sr + 40 n

139
56

Xe +

94
36

144
55

Xe +

90
37

Kr + 301 n

Rb + 201 n
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Nuclear Fission; Nuclear Reactors


When the uranium-235 nucleus splits, it releases two or three
neutrons. These neutrons are absorbed by other uranium-235
nuclei, which then release even more neutrons.
A nuclear chain reaction is
a self-sustaining series of
fissions caused by the
of neutrons released from
nuclear fissions.

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A nuclear fission reactor is a device that permits a controlled


chain reaction of nuclear fission.
Fuel rods contain the fissionable material. They alternate with
control rods that absorb neutrons.

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Nuclear Fusion
Energy is released when light nuclei combine into a heavier
nucleus in a fusion reaction. These reactions have been observed
in the laboratory using particle accelerators.
For the nuclei to react, the bombarding nuclei must have enough
kinetic energy to overcome the repulsion between positive nuclei.
The energy required is not practically available at this time.

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