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TABLE OF C ONTENTS

R ADIOACTIVITY AND N UCLEAR E QUATIONS

C HEM 16 G ENERAL C HEMISTRY 1


13 C HANGES IN THE N UCLEUS

PATTERNS OF N UCLEAR S TABILITY


N UCLEAR T RANSMUTATIONS
R ATES OF R ADIOACTIVE D ECAY

Dr. Gil C. Claudio


University of the Philippines, Diliman

First Semester 2014-2015

D ETECTION OF R ADIOACTIVITY
E NERGETICS OF N UCLEAR R EACTIONS
N UCLEAR P OWER : F ISSION
N UCLEAR P OWER : F USION
E FFECT OF N UCLEAR R ADIATION ON M ATTER

R EFERENCES

References of these notes

General Chemistry, 10th ed, by Ralph H. Petrucci, F. Geoffrey


Herring, Jeffy D. Madura, and Carey Bisonnette.

Chemistry: The Central Science, 13th ed., by Theodore


L. Brown, H. Eugene LeMay Jr., Bruce E. Bursten, Catherine
J. Murphy, Patrick M. Woodward, and Matthew W. Stoltzfus.

N UCLEAR C HEMISTRY

Nuclear chemistry is the study of nuclear reactions, with an


emphasis on their uses and their effects on biological systems.

energy and medical applications

used to help determine the mechanisms of chemical reactions,


to trace the movement of atoms in biological systems and the
environment, and to date historical artifacts.

I SOTOPES AND N UCLIDES


Atoms with the same atomic number but different mass numbers
are known as isotopes.

The mass number is the total number of nucleons in the


nucleus.

Isotopes of the same element have different mass numbers,


different natural abundances, and different stabilities.

E.g., the three naturally occurring isotopes of uranium are


235
uranium-234 ( 234
92U, trace amounts), uranium-235 ( 92U,
0.7%), and uranium-238 ( 238
92U, 99.3%).

A nuclide is a nucleus containing a specified number of protons


and neutrons.

R ADIOACTIVITY

Radioactivity is a phenomenon in which small particles of matter


( or particles) and/or electromagnetic radiation ( rays) are
emitted by unstable atomic nuclei.

Proposed by Marie Curie to describe the emission of ionizing


radiation by some of the heavier elements. Ionizing radiation
interacts with matter to produce ions. Thus the radiation is
sufficiently energetic to break chemical bonds.

Some ionizing radiation is particulate (consisting of particles), and


some is nonparticulate.

particulate: , , and particles

Nuclides that are radioactive are called radionuclides, and


atoms containing these nuclei are called radioisotopes.

N UCLEAR E QUATIONS

A nuclear equation represents the changes that occur during a


nuclear process. The target nucleus and bombarding particle are
represented on the left side of the equation, and the product
nucleus and ejected particle on the right side. A nuclear equation
is written to conform to two rules:
1. The sum of mass numbers must be the same on both sides.
2. The sum of atomic numbers must be the same on both sides.

A LPHA PARTICLES
An alpha () particle is a combination of two protons and two
neutrons identical to the helium ion ( 4He2+ ). Alpha particles are
emitted in some radioactive decay processes.

They produce large numbers of ions via their collisions and


near collisions with atoms as they travel through matter, but
their penetrating power is low.

Because they have a positive charge, they are deflected by


electric and magnetic fields.

A reaction that produces an particle is also called an alpha


decay.
238
92U

234
90Th

+ 42He

B ETA PARTICLES

B ETA E MISSION

A beta particle ( particle) is an electron emitted as a result of


the conversion of a neutron to a proton in certain atomic nuclei
undergoing radioactive decay.

particles are are electrons that originate from the nuclei of


atoms in nuclear decay processes

extremely energetic and do not end up in an orbital of the


decaying atom

represented as either

their mass is exceedingly small relative to a nucleon

they have a negative (-) charge, and are thus deflected by


electric and magnetic fields

greater penetrating power through matter than particles

0
-1e

Iodine-131 is an isotope that undergoes decay by beta emission


131
53I

or

G AMMA R ADIATION

1
0n

1
1H

It changes neither the atomic number nor the mass number of


a nucleus

131
54Xe

0
-1e

0
-1e

n p +

or

S UMMARY OF P ROPERTIES

Gamma () rays are a form of electromagnetic radiation of high


penetrating power emitted by certain radioactive nuclei.

Beta emission is equivalent to the conversion of a neutron to a


proton.

charge

2+

-1

0
0

represented as either 00 or simply .

mass (g)

6.64 1024

9.11 10 28

Gamma radiation usually accompanies other radioactive


emission because it represents the energy lost when the
nucleons in a nuclear reaction reorganize into more stable
arrangements.

relative penetrating
power
nature of radiation

100

10,000

Electrons

High-energy
photons

Often gamma rays are not explicitly shown when writing


nuclear equations.

4
2He

nuclei

P OSITRON E MISSION

E LECTRON C APTURE

A positron (+ , +10 , or +10e) is a positive electron emitted as a


result of the conversion of a proton to a neutron in a radioactive
nucleus.

same mass as electron, opposite in charge

positron emission causes the atomic number of the reactant


to decrease by 1

Examples of decays by positron emission


11
6C

11
5B

0
+1e

1
0n

0
+1e

30
15P

30
14Si

0
+1e

Generally
1
1p

or

When an electron from a higher quantum level drops to the


energy level vacated by the captured electron, X radiation is
emitted.

Some examples are


81
37Rb

0
-1e

Particles found in nuclear reactions


symbol
1
0n or n
1
1H or p
0e
4
2He or
0

-1e or
0
+
+1e or

81
36Kr

202
81Tl

0
-1e

202
80Hg

Electron capture, like positron emission, has the effect of


converting a proton to a neutron:
1
1p

p n + +

PARTICLES IN N UCLEAR R EACTIONS

particle
neutron
proton
electron
alpha particle
beta particle
positron

Electron capture is a mode of radioactive decay in which an


inner-shell orbital electron is captured by the nucleus.

0
-1e

1
0n

T YPES OF R ADIOACTIVE D ECAY

type

nuclear equation

alpha decay

A
ZX

A-4
Z -2Y

beta emission

A
ZX

A
Z +1Y

positron emission

A
ZX

A
Z -1Y

electron capture

A
ZX

0
-1e

+ 42He
+

0
-1e
0
+1e

A
Z -1Y

change
in Z

change
in A

-2

-4

+1

unchanged

-1

unchanged

-1

unchanged

R ADIOACTIVE D ECAY M ODES

N EUTRON - TO -P ROTON R ATIO

EC

Neutrons are involved in the strong nuclear force that keep


positively charged protons within a small volume.

+
p

n
N

As the number of protons in a nucleus increases, there is an


ever greater need for neutrons to counteract the protonproton
repulsions.

at Z 20, nneutrons nprotons

at Z > 20, nneutrons > nprotons

to create a stable nucleus increases more rapidly than the


number of protons

Thus, the neutron-to-proton ratios of stable nuclei increase


with increasing atomic number

E.g.,

Parent
atom




Z

12
6C

(n/p = 1),

55
22Mn

(n/p = 1.2),

197
79Au

(n/p 1.49)

en.wikipedia.org/wiki/File:Radioactive decay modes.svg

N EUTRON - TO -P ROTON R ATIO

B ELT OF S TABILITY

The dark blue dots in the figure represent stable (nonradioactive)


isotopes. The region of the graph covered by these dark blue dots
is known as the belt of stability.

en.wikipedia.org/wiki/File:Table isotopes en.svg

The belt of stability ends at element 83 (bismuth).

All nuclei with 84 or more protons are radioactive.

R ADIOACTIVE D ECAY PATTERS

P REDICTING M ODES OF N UCLEAR D ECAY


BLBMWS 13 E , E XERCISE 21.3, P 916

The type of radioactive decay that a particular radionuclide


undergoes depends largely on how its neutron-to-proton ratio
compares with those of nearby nuclei that lie within the belt of
stability. Three general situations:
1. Nuclei above the belt of stability (high neutron-to-proton
ratios). Increase stability via emitting a beta particle.
2. Nuclei below the belt of stability (low neutron-to-proton
ratios). Increase stability by increasing the number of
neutrons via either positron emission or electron capture.

Predict the mode of decay of


1. carbon-14,
2. xenon-118.
ANSWERS
1. emit a beta particle to decrease the n/p ratio:
14
6C

3. Nuclei with atomic numbers 84. These heavy nuclei tend


to undergo alpha emission.

R ADIOACTIVE D ECAY S ERIES

14
7N

0
-1e

2. either positron emission or electron capture


118
54Xe

118
54Xe

118
53I

0
-1e

0
+1e
118
53I

M AGIC N UMBERS FOR N UCLEAR S TABILITY


Two further observations can help us to predict stable nuclei:

A radioactive decay series (or radioactive decay chain, or


nuclear disintegration series is a succession of individual steps
whereby an initial radioactive isotope is ultimately converted to a
stable isotope.

cannot gain stability by a single emission, occurs in a series of


successive emissions

Three such series occur in nature: uranium-238 to lead-206,


uranium-235 to lead-207, and thorium-232 to lead-208. All of
the decay processes in these series are either alpha emissions
or beta emissions.

1. Nuclei with the magic numbers of 2, 8, 20, 28, 50, or 82


protons or 2, 8, 20, 28, 50, 82, or 126 neutrons are generally
more stable than nuclei that do not contain these numbers of
nucleons.
2. Nuclei with even numbers of protons, neutrons, or both are
more likely to be stable than those with odd numbers of
protons and/or neutrons.
60% of stable nuclei have an even number of both protons
and neutrons, whereas less than 2% have odd numbers of both.

These can be understood in terms of the shell model of the


nucleus.

nucleons reside in shells analogous to the shell structure for


electrons in atoms, where certain numbers of electrons
correspond to stable filled-shell electron configurations.

P ROTONS AND N EUTRONS PAIRS

N UCLEAR T RANSMUTATIONS

Evidence also suggests that pairs of protons and pairs of neutrons


have a special stability, analogous to the pairs of electrons in
molecules.

Thus stable nuclei with an even number of protons and/or


neutrons are far more numerous than those with odd numbers.

In some nuclear reactions, the nucleus decays spontaneously. A


nucleus can also change identity if it is struck by a neutron or by
another nucleus. Nuclear reactions induced in this way are known
as nuclear transmutations.
In 1919, Ernest Rutherford performed the first conversion of one
nucleus into another, using alpha particles emitted by radium to
convert nitrogen-14 into oxygen-17
14
7N

S HORTHAND N OTATION

+ 42He

17
8O

+ 11H

or

14
7N

17
8O

+p

W RITING A B ALANCED N UCLEAR E QUATION


BLBMWS 13 E , E XAMPLE 21.4, P 918

The shorthand notation to represent nuclear transmutations


14
7N

(,p)

Write the balanced nuclear equation for the process summarized as


27
24
13Al(n, ) 11Na.

17
8O

target nucleus
bombarding particle
ejected particle
product nucleus

14
7N

p
17
8O

ANSWER
27
13Al

+ 10n

24
11Na

+ 42He

or

27
13Al

+n

24
11Na

A CCELERATING C HARGED PARTICLES

F ERMI N ATIONAL A CCELERATOR L ABORATORY

A particle accelerator a device that uses strong magnetic and


electrostatic fields to accelerate charged particles.

Also called cyclotron, synchrotron, and atom smashers.

Alpha particles and other positively charged particles must


move very fast to overcome the electrostatic repulsion
between them and the target nucleus.

The charged particles can be manipulated by electric and


magnetic fields.

They pass through tubes kept at high vacuum to avoid


inadvertent collisions with any gas-phase molecules.

en.wikipedia.org/wiki/File:Fermilab.jpg

R EACTIONS I NVOLVING N EUTRONS

Neutrons, because they are neutral, are not repelled by the nucleus
and do not need to be accelerated to cause nuclear reactions. The
neutrons are produced in nuclear reactors.

T RANSURANIUM E LEMENTS
Transuranium elements are elements that follow uranium in the
periodic table.

238
1
239
239
0
92U + 0n 92U 93Np + -1e
239
1
239
0
93Np + 0n 94Pu + -1e

For example, synthesis of cobalt-60 from iron-58


58
26Fe
59
27Co

+ 10n
59
26Fe
+ 10n

59
26Fe
59
27Co
60
27Co

Elements 93 (neptunium, Np) and 94 (plutonium, Pu) were


produced in 1940 by bombarding uranium-238 with neutrons.

Elements with still larger atomic numbers are normally formed


in small quantities in particle accelerators. For example, by
using alpha particles

Other elements can be used.

0
-1e

239
94Pu
208
82Pb

+ 42He
+

70
30Zn

242
96Cm

+ 10n

277
112Cn

+ 10n

R ADIOACTIVE D ECAY
Radioactive decay is a first-order kinetic process, which has a
characteristic half-life.
The half-life t1/2 of a reaction is the time required for one-half of a
reactant to be consumed. In a nuclear decay process, it is the time
required for one-half of the atoms present in a sample to undergo
radioactive decay.

Half-lives as short as millionths of a second and as long as


billions of years are known.

unaffected by external conditions such as temperature,


pressure, or state of chemical combination, thus they cannot
be rendered harmless by chemical reaction or by any other
practical treatment

C ALCULATION OF H ALF -L IVES

H ALF -L IVES AND D ECAY T YPES


The half-lives and type of decay for several natural (N) or synthetic
(S) radioisotopes
N/S
N
N
N
N
N
S
S
S
S

Isotope
238
92U
235
92U
232
90Th
40
19K
14
6C
239
94Pu
137
55Cs
90
38Sr
131
53I

half-life (yr)
4.5 109
7.0 108
1.4 101 0
1.3 109
5700
24,000
30.2
28.8
0.022

type of decay
alpha
alpha
alpha
beta
beta
alpha
beta
beta
beta

R ADIOACTIVE D ECAY L AW

BLBMWS 13 E , E XERCISE 21.5, P 921

The half-life of cobalt-60 is 5.27 yr. How much of a 1.000-mg


sample of cobalt-60 is left after 15.81 yr?
ANSWER: 0.125 mg

The radioactive decay law states that the rate of decay of a


radioactive materialthe activity, Ais directly proportional to the
number of atoms present.
The rate for a first-order kinetic process is
Rate = kN
where N is the number of radioactive nuclei and k is the decay
constant.

A CTIVITY AND D ECAY R ATE

F IRST-O RDER R ATE L AW


A first-order rate law (Rate = kN) can be transformed into
ln

The rate at which a sample decays is called its activity.

The becquerel (Bq) is the SI unit for expressing activity. A


becquerel is defined as one nuclear disintegration per second.

An older, but still widely used, unit of activity is the curie


(Ci), defined as 3.7 1010 disintegrations per second, which is
the rate of decay of 1 g of radium.

Nt
= kt
N0

where t is the time interval of decay, k is the decay constant, N0 is


the initial number of nuclei (at time zero), and Nt is the number
remaining after the time interval.
The relationship between the decay constant k and half-life t1/2 is
k=

0.693
t1/2

using the value ln(Nt /N0 ) = ln(0.5) = 0.693 for one half-life.

C ALCULATING THE A GE OF O BJECTS

R ADIOACTIVE D ECAY AND T IME

BLBMWS 13 E , E XERCISE 21.6, P 924

BLBMWS 13 E , E XERCISE 21.7, PP 924-925

If we start with 1.000 g of strontium-90, 0.953 g will remain after


2.00 yr.
A rock contains 0.257 mg of lead-206 for every milligram of
uranium-238. The half-life for the decay of uranium-238 to
lead-206 is 4.5 109 yr. How old is the rock?
ANSWER: 1.7 109 yr

1. What is the half-life of strontium-90?


2. How much strontium-90 will remain after 5.00 yr?
3. What is the initial activity of the sample in becquerels and
curies?
ANSWERS:
1. t1/2 = 28.8 yr
2. Nt = 0.887 g
3. 5.1 102 disintegrations/s or 1.4 102 Ci

G EIGER C OUNTER

G EIGER C OUNTER
Cathode
Input
Window

Radioactivity can be detected and measured by a Geiger counter.

Radiation is able to ionize matter. The ions and electrons


produced by the ionizing radiation permit conduction of an
electrical current.

A current pulse between the anode and the metal cylinder


occurs whenever entering radiation produces ions. Each pulse
is counted in order to estimate the amount of radiation.

Gamma
Radiation
Counter

Resistor

Voltage
Source

commons.wikimedia.org/wiki/File:Geiger Mueller Counter with Circuit-en.svg

E NERGY OF N UCLEAR R EACTIONS

In order to understand the great amount of energy released in


nuclear reactions as compared to chemical reactions, we start with
Einsteins equation from the theory of relativity that relates mass
and energy: E = mc 2

The mass changes in chemical reactions are too small to


detect, thus mass is conserved. E.g., the mass change in the
combustion of 1 mol of CH4 is 9.9 109 g.

The mass changes and the associated energy changes in


nuclear reactions are much greater than those for chemical
reactions.

M ASS AND E NERGY C HANGE IN U RANIUM -238


D ECAY
Given the alpha decay of uranium-238
238
92U

234
90Th

+ 42He

The mass change is the total mass of the products minus the total
mass of the reactants.
233.9942 g + 4.0015 g 238.0003 g = 0.0046 g
The energy change per mole associated with this reaction is
E

= (mc 2 ) = c 2 m
= (2.9979 108 m/s)2 0.0046 g = 4.1 1011 J

M ASS D EFECT

N UCLEAR B INDING E NERGY

Scientists discovered in the 1930s that the masses of nuclei are


always less than the masses of the individual nucleons of which
they are composed.

mass of 42He is 4.00150 amu, mass of 1 p is 1.00728 amu,


mass of 1 n is 1.00866 amu
mass 2 p + 2 n > mass 42He, with a mass difference of
0.03038 amu

The mass difference between a nucleus and its constituent


nucleons is called the mass defect.

S OME B INDING E NERGIES

Energy + 42He 2 11H + 2 10n


The mass change for the conversion of helium-4 into separated
nucleons is m = 0.03038 amu. Using E = mc 2 , thus
E = c 2 m = 4.534 1012 J
The energy required to separate a nucleus into its individual
nucleons is called the nuclear binding energy.

N UCLEAR S TABILITY AND B INDING E NERGY

Mass (m) defects and binding energies (BE) for three nuclei
(masses in amu, energy in J).
m of nucleus
mtot of nucleons
mass defect m
BE
BE per nucleon

Energy must be added to a nucleus to break it into separated


protons and neutrons

4
2He

56
26Fe

238
92U

4.00150
4.03188
0.03038
4.53 1012
1.13 1012

55.92068
56.44914
0.52846
7.90 1011
1.41 1012

238.00031
239.93451
1.93420
2.89 1010
1.21 1012

Values of BE per nucleon can be used to compare the stabilities of


different combinations of nucleons.

BE per nucleon at first increases until 1.4 1012 J for nuclei


with A A(iron-56).
BE then decreases to about 1.2 1012 J for very heavy
nuclei
Nuclei of intermediate mass numbers are more tightly bound,
thus more stable, than those with either smaller or larger mass
numbers.

F ISSION AND F USION

This trend has two significant consequences


1. Heavy nuclei gain stability and therefore give off energy if they
are fragmented into two mid-sized nuclei. This process is
known as fission. Used to generate energy in nuclear power
plants.
2. Due to the sharp increase in the graph for small mass
numbers, even greater amounts of energy are released if very
light nuclei are combined, or fused together, to give more
massive nuclei. This fusion process is the essential
energy-producing process in the sun and other stars.

C HAIN R EACTIONS

Initial absorption of the neutron by the nucleus. The resulting


more massive nucleus is often unstable and spontaneously
undergoes fission.

Slow-moving neutrons are required, fast neutrons tend to


bounce off the nucleus.

Each reaction produces more neutrons, causing further fission,


causing a chain reaction.

The number of fissions and the energy released quickly


escalate, and if the process is unchecked, the result is a
violent explosion.

F ISSION OF U RANIUM -235

Two ways that the uranium-235 nucleus splits are


1
0n

235
92U

137
52Te
142
56Ba

1
+ 97
40Zr + 2 0n
1
+ 91
36Kr + 3 0n

The nuclei produced are called the fission products.

also radioactive and undergo further nuclear decay


fission products of 235
92U more than 200 isotopes of 35
elements, most of them radioactive

C RITICAL AND S UPERCRITICAL M ASS

The minimum amount of fissionable material large enough to


maintain a chain reaction with a constant rate of fission is called
the critical mass.

The critical mass of uranium-235 is about 50 kg for a bare


sphere of the metal.

If more than a critical mass of fissionable material is present, very


few neutrons escape. The chain reaction thus multiplies the
number of fissions, which can lead to a nuclear explosion. A mass
in excess of a critical mass is referred to as a supercritical mass.

N UCLEAR R EACTORS

F USION IN THE S UN

Nuclear power plants use nuclear fission to generate energy. Four


principal components of the core
1. Fuel elements. A fissionable substance, e.g., uranium-235.
2. Control rods. Materials that absorb neutrons, such as
boron-10 or an alloy of silver, indium, and cadmium. These
rods regulate the flux of neutrons to keep the reaction chain
self-sustaining and also prevent the reactor core from
overheating.

Spectroscopic studies indicate that the mass composition of the


Sun is 73% H, 26% He, and only 1% all other elements. The
following reactions are among the numerous fusion processes
believed to occur in the Sun:
1
1
1H + 1H
1
2
1H + 1H
3
3
2He + 2He
3
1
He
+
2
1H

3. Moderator. These slow down the neutrons ( few km/s) so


that they can be captured more readily by the fissionable
nuclei. E.g., water or graphite.

2
0
1H + +1e
3
2He
4
1
2He + 2 1H
4
0
2He + +1e

4. Primary coolant. Transports the heat generated by the


nuclear chain reaction away from the reactor core. E.g. water.

F USION AS AN E NERGY S OURCE


Fusion is appealing as an energy source because of the availability
of light isotopes on Earth and because fusion products are
generally not radioactive. Despite this fact, fusion is not presently
used to generate energy.

Extremely high temperatures and pressures are needed to


overcome the electrostatic repulsion between nuclei in order to
fuse them. Fusion reactions are therefore also known as
thermonuclear reactions. The lowest temperature required
for any fusion is about 40,000,000 K, the temperature needed
to fuse deuterium and tritium.
No known structural material is able to with stand the
enormous temperatures necessary for fusion.

Even with the current technology, scientists have not yet been able
to generate more power than is consumed over a sustained period
of time.

I ONIZING R ADIATION

Radiation energy can cause atoms in the matter to be either


excited or ionized.

Ionizing radiation is radiation that causes ionization. It is far


more harmful to biological systems than nonionizing radiation

Nonionizing radiation is low in energy and does not cause


ionization. Slow-moving. E.g., radiofrequency electromagnetic
radiation.

I ONIZATION OF WATER
Most living tissue contains at least 70% water by mass. Water
absorbs most of the energy of the radiation. Thus, it is common to
define ionizing radiation as radiation that can ionize water, > 1216
kJ/mol.

, , rays, X-rays and higher-energy ultraviolet radiation are


forms of ionizing radiation.

When ionizing radiation passes through living tissue, electrons are


removed from H2 O, forming highly reactive H2 O+ ions, which then
produces the unstable and highly reactive free radical OH (hydroxyl
radical).
H2 O+ + H2 O H3 O+ + OH
In cells and tissues, OH can attack biomolecules to produce new
free radicals, which in turn attack yet other biomolecules. Thus a
few OH radicals can initiate a large number of chemical reactions
that are ultimately able to disrupt the normal operations of cells.