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Chapter 21:
Nuclear Chemistry

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Chemistry: The Molecular Nature


of Matter, 6E
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How are atoms formed?


Big BangIntense heat ~109 K

Cooled quickly to 106 KT of stars


e, p+, no formed and joined into nucleiatoms
Mostly H and He (as in our sun)
Rest of elements formed by nuclear reactions

Fusiontwo nuclei come together to form


another heavier nucleus
+

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Fissionone heavier nucleus splits into


lighter nuclei
+

Various other types of reactions


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Nuclear Shorthand

Nucleons

Subatomic particles found in the nucleus


Protons (p+)
Neutrons (no)

Nuclide

Specific nucleus with given atomic number (Z)

Atomic Number (Z)

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Number of protons in nucleus


Determines chemical properties of nuclide
Z = p+

Mass Number (A)mass of nuclide


A = no + p +
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Shorthand for Writing Nuclides


Where X = atomic symbol
A
ZX

Ex.

Cd

113
48

Th

230
90

In the neutral atom: e = p+ = Z


Isotopes
Nuclides with same Z (same number of p+), but
different A (different no)

1
1

2
1

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Hydrogen
1 p+

3
1

Deuterium

Tritium

1 p+ + 1 n o 1 p+ + 2 n o

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Radioactivity

Radioactive isotopes

Isotopes with unstable atomic nuclei


Emit high energy streams of particles or
electromagnetic radiation

Radionuclides

Another name for radioactive isotopes


Undergo nuclear reactions

Uses

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Dating of rocks and ancient artifacts


Diagnosis and treatment of disease
Source of energy
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Mass Not Always Constant


Mass of particle not constant under all
circumstances
It depends on velocity of particle relative to
observer
As approaches speed of light, mass decreases
m =

mo

1 (v / c ) 2

When v goes to zero

Particle has no velocity relative to observer


v/c 0
Denominator 1
and m = mo

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m = mass of particle
v = velocity of particle
m = rest mass
c = speed of light

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Why dont we observe mass change?


m=

mo

1 (v / c ) 2

In lab and ordinary life, velocity of particle is


small
Only see mass vary with speed as velocity
approaches speed of light, c
As v c,

(v/c) 0 and m

In lab, m = mo within experimental error

Difference in mass too small to measure directly

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Scientists began to see relationship between


mass and total energy
Analogous to potential and kinetic energies
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Law of Conservation of Mass and


Energy

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Mass and energy can neither be created nor


destroyed, but can be converted from one to
the other.
Sum of all energy in universe and all mass
(expressed in energy equivalents) in universe
is constant
Einstein Equation
E = (mo)c2
Where c = 2.9979 x 108 m/s
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Mass Defect

Rest mass of nuclide is always less than sum of


masses of all individual nucleons (neutrons and
protons) in that same nuclide
Mass is lost upon binding of neutrons and protons into
nucleus

When nucleons come together, loss of mass translates


into release of enormous amount of energy by
Einstein's relation
Energy released = Nuclear Binding Energy

Nuclear Binding Energy

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Amount of energy must put in to break apart


nucleus
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What is Mass Loss?

For given isotope of given Z and A

m = m nucleus m nucleons
or

) (

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m = m isotope Z m e N m n + Z m p

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Ex.1. Binding Energy Calculation


What is the binding energy of 7Li3+ nucleus?

3 p+ + 4 no

7 3+
3 Li

+ E

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Step 1. Determine mass loss or mass defect


A. Determine mass of nucleus
mass of 7Li3+ = m(7Li isotope) 3 me
= 7.016003 u 3(0.0005485 u)
= 7.0143573 u
B. Determine mass of nucleons
mass of nucleons = 3 mp + 4 mn
= 3(1.007276470 u) + 4(1.008664904 u)
= 7.056489026 u
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Ex.1. (cont.) Binding Energy


Calculation

C. m = mnucleus mnucleons
= 7.0143573 u 7.056489026 u
= 0.0421317 u
= mass lost by nucleons when they form nucleus
Step 2. Determine energy liberated by this
change in mass

E = (mo)c2

E = ( 0.0421217u ) 1.6605402 10 27 kg / u
2
1J
8
* 2.997925 10 m / s
kg m 2 / s 2
E = 6.287817 x 1012 J/atom

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Ex. 1. (continued)

E = 6.287817 x 1012 J/atom *

6.0221367 x 1023 atoms/mole


E = 3.78655 x 1012 J/mole
= 3.78655 x 109 kJ/mole

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Compare this to:


104 105 J/mol (102 103 kJ/mol) for chemical
reactions
Nuclear ~ 1 10 million times larger than
chemical reactions!!
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MeV (Energy Unit)

Nuclear scientists find it convenient to use a


different Energy unit: MeV (per atom)
Electron volt (eV)

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Energy required to move e across energy potential


of 1 V
1 eV = 1.602 1019 J
M(mega) = 1 x 106
So 1 MeV = 1 106 eV
1 MeV = 1.602 x 1013 J

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Ex. 1. but in MeV

For Ex. 1. Converting E to MeV gives


EB

6.287817 10 12 J/atom

=
1.602177 10 13 J/MeV

= 39.245 MeV/atom

Often wish to express binding energy per


nucleon so we can compare to other nuclei
For Li3+ with 3 1p and 4 0n this would be
3+

) 39.245MeV
=
= 5.61MeV
nucleon
7

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E B (Li

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Ex. 2 Calculate E released


The overall reaction in the sun responsible for
the energy it radiates is

1
1H

4
2 He

+2

0 +
1e

How much energy is released by this reaction


in kJ/mole of He?

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m(1H) = 1.00782 u
m(4He) = 4.00260 u
m(0+) = 0.00054858 u
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Ex. 2 (cont.)

m = mproducts mreactants

m = m(4He) + 2m(0e+) 4m(1H)

m = 4.00260 u + 2(0.00054858 u) 4(1.00782 u)


m = 0.02758 u

E = ( 0.02758u ) 1.6605402 10 27 kg / u
2
1J
8
2.997925 10 m / s
2
2
kg m / s

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(6.0221367 10

23

atoms / mol

E = 2.48 x 1012 J/mol


= 2.48 x 109 kJ/mol
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Your Turn!

Determine the binding energy, in kJ/mol and


MeV/atom, for an isotope that has a mass defect of
0.025861 u.

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A. -2.3243 x 109 kJ/mol; 24.092 MeV/atom


B. -3.8595 x 10-12 kJ/mol; 24.092 MeV/atom
C. -7.7529 kJ/mol; 8.03620x 10-8 MeV/atom
D. -2.3243 x 109 kJ/mol; 4.1508 x 10-2 MeV/atom

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Your Turn! - Solution

E = ( 0.025861u ) (1.6605402 10 27 kg / u )

* 2.997925 10 m/s

1J
kgm2 /s 2

= 3.8595 x 10 12 J/atom

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23 atoms
12
=
3.8595 x 10 atom 6.0221367 x 10

mol

J
12
9 kJ
or -2.3243 x 10
2.3243 x 10
mol
mol

J
1 MeV
MeV

12
= 24.092
3.8595 x 10

-13

atom 1.602 x 10 J
atom

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Binding Energies per Nucleon

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Divide binding
energy EB by
mass number,
EB/A
Get binding
energy per
nucleon

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Implications of Curve

Most EB/A in range of 6 9 MeV (per nucleon)


Large binding energy EB/A means stable
nucleus
Maximum at A = 56
56Fe largest known EB/A
Most Thermodynamically stableTD sink

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Nuclear mass number (A) and overall charge


are conserved in nuclear reactions
Lighter elements undergo fusion to form more
stable nuclei

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Implications of Curve

Ex. Fusion
2
3
1H + 1H

He + n + 17.6 MeV

4
2

1
0

Researchers are currently working to get fusion to


occur in lab
Heavier elements undergo fission to form more
stable elements

Ex. Fission
235
1
U
+
92
0n

Ba +

142
56

Kr + 3 01n

91
36

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Reactions currently used in bombs and power


plants (238U and 239Pu)
As stars burn out, they form elements in center of
Periodic Table around 56Fe
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Radioactivity

Spontaneous emission of high energy


particles from unstable nuclei
Spontaneous emission of fundamental particle or
light
Nuclei falls apart without any external stimuli

Discovered by Becquerel (1896)


Extensively studied by Marie Curie and her
husband Pierre (1898 early 1920's)

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Initially worked with Becquerel

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Fun Facts

Marie and Pierre Curie discovered Polonium


and Radium
Nobel Prize in Physics 1903
For discovery of Radioactivity
Becquerel, Marie and Pierre Curieall three shared

Nobel Prize in Chemistry 1911

For discovery of Radium and its properties


Marie Curie only

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Marie Curie - first person to receive two Nobel


Prizes and in different fields
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Discovery of Radioactivity

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Initially able to
observe 3 types of
decay
Labeled them , ,
rays (after 1st three
letters of Greek
alphabet)
If they pass through
an electric field,
very different
behavior
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Discovery of Radioactivity

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rays attracted to
pole
positively charged
rays attracted to +
pole
negatively charged
rays not attracted to
either
not charged

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Nuclear Equations

Used to symbolize decay of nucleus

Ex.

90
+
parent
daughter
238U
92

234Th

4
2

He

Produce new nuclei so need separate rules


to balance
Balancing Nuclear Equations

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a. Sum of mass numbers (A, top) must be same


on each side of arrow
b. Sum of atomic numbers (Z, bottom) must be
same on each side of arrow
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Types of Spontaneous Emission


1. Alpha () Emission
= He nucleus
=2n+2p
A = 4 and Z = 2

Daughter nuclei has:

A = 4
Z = 2
Very common mode of decay
if Z > 83 (large radioactive nuclides)
Most massive particle

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A by 4
Z by 2

Ex.

234
92 U

230
90Th

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4
2

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Balancing Nuclear Equations


1. The sum of the mass numbers (A;
superscripts) on each side of the arrow must
be the same
2. The sum of the atomic numbers (Z;
subscripts; nuclear charge) on each side of
the arrow must be the same
230
4
Ex. 234
U

Th
+
92
90
2

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A: 234 = 230 + 4
Z: 92 = 90 + 2
226
88 Ra

222
86 Rn

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4
2 He

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2. Beta ( or e) Emission

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Emission of e
Mass number A = 0 and charge Z = 1
But How? NO e's in nucleus!
If nucleus (n rich)nuclide too heavy
1
n 1p + 0e + ~

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Beta ( or e) Emission

n p +

1
0

1
1

~
e +

0
1

Charge conserved, but not mass m E


Ejected e has very high KE + emits

Antineutrino ~
variable energy particle

Accounts for extra E generated


235
92U

214
82 Pb

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Ex.

0
1

214
83 Bi

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235
93 Np

+ ~

0
1 e

+~

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3. Gamma () Emission

Emission of high energy photons


Often accompanies or emission
Occurs when daughter nucleus of some
process is left in excited state
Use * to denote excited state

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Nuclei have energy levels analogous to those


of e in atoms
Spacing of nuclear E levels much larger
light emitted as -rays
Ex. 137
137
56 Ba

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56 Ba

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4. Positron (+ or e+) Emission


Emission of e+
Positive electron
Where does + come from?
If nucleus (n poor)
Nuclide too light
1
1p

1
0n

0
+1e

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Balanced for charge,


but NOT for mass
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4. Positron (+ or e+) Emission


Product side has much greater mass!
Reaction costs energy
Emission of Neutrino
Variable energy particle
Equivalent of antineutrino but in realm of
antimatter

e+ emission only occurs if daughter nucleus


is MUCH more stable than parent

Pe

38
19 K

0
+1 e

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18 Ar

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4. Positron (+or e+) Emission


What happens to e+?

Collides with electron to give matter


anti-matter annihilation and two high
energy -ray photons m E
0
1 e

0
+ 1e

Annihilation radiation photons


Each with E = 511 keV

What is antimatter?

Pe

Particle that has counterpart among


ordinary matter, but of opposite
charge
High energy light, massless
Detect by characteristic peak in
-ray spectrum
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5. Electron Capture (EC)


e in 1s orbital

Lowest Energy e
Small probability that e is
near nucleus
e actually passes through
nucleus occasionally
1
0
1
p
+
e

If it does: 1
0n
1
Net effect same as e+ emission
electron capture

Pe

195
0
Au
+
79
1 e

Jespersen/Brady/Hyslop

195
78 Pt

+ X rays +

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Types of Spontaneous Emission


6. Neutron Emission = ( 01n )

Fairly rare
Occurs in n rich nuclides
Does not lead to isotope of different element
137
53 I

136
53 I

1
0n

7. Proton Emission = (11p )

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Very rare
57
30 Zn

56
29 Cu

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1
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Types of Spontaneous Emission


8. Spontaneous Fission
NO stable nuclei with Z > 83
Several of largest nuclei simply fall apart
into smaller fragments
Not just one outcome, usually several
differentsee distribution

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256
100 Fm

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125
49 In

120
47 Ag

131
51Sb

136
53I

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SummaryCommon Processes
1. Alpha () Emission

4
2 He

Very common if Z > 83

2. Beta () Emission e

Common for n rich nuclidesbelow belt of stability

3. Positron (+) Emission e+

Common for n poor nuclidesabove belt of stability

4. Electron Capture (EC)

Occurs in n poor nuclides, especially if Z > 40

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5. Gamma () Emission

Occurs in metastable nuclei (in nuclear excited state)

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Learning Check

Complete the following table which refers to


possible nuclear reactions of a nuclide:
Emission Z = n
p

2
2

A New
Element?

yes

+1

yes

+1

+1

yes

+1

+1

yes

no

Pe

EC

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Learning Check

Balance each of the following equations


4
239
235
2 He
a. 94 Pu 92 U + ____
b.

131
53 I

c.

27
15 P

d.

40
20 Ca

f.

88
38 Sr

27
14 Si

238
92 U

1
0n

84
36 Kr

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e.

233
92 U

131
54 Xe

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0
1e +
____

0
1e +
+
____

70
30 Zn

72
30 Zn

+ 4

+ 2

116
46 Pd

1
0n

1
0n

204
82 Pb
____

160
62 Sm
____

+ E

+E

56
28 Ni
____

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Your Turn!

What is the missing species, mn X ,in the following


nuclear reaction?
n
m

Cf

239
94

Pu

238
94

Pu

242
96

Cm + 01 n

Am

Pe

A.
B.
C.
D.

247
98
238
95

X + 42 He

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What Holds Nucleus Together?


Consider nucleus

no + p+ in close proximity
Strong p+ + p+ repulsions
no spread p+'s apart
n/p ratio as Z

Strong Forces

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Force of attraction between nucleons


Holds nuclei together
Overcomes electrostatic repulsions between
protons
Binds protons and neutrons into nucleus
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Table of Nuclides

Chart where Rows = different Z (At. #)


Columns = different N (# n)
Symbol entered if element is known
Stable nuclei

Natural abundance entered below symbol


Shaded area
Trend of stable nuclei = Belt of Stability
~ Z = N (for 1 to 20)

Unstable nuclei

Pe

Give type(s) of radioactive decay (spontaneous)


Outer edges, most of atoms
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# of neutrons (N = # on)

Table of Nuclides

Atomic number (Z = # of protons)


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Table of Nuclides

Note: only a small corner of table is


shown. (complete is in CRC)
Shaded area = Stable Nuclei
Trend of stable nuclei = diagonal line =

Belt of Stability

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~ Z = N (for 1 to 20)

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Belt of Stability

1.5n:1p
Stable nuclide, natural
: Unstable nuclide, natural
Unstable nuclide, synthetic
1.4n:1p
Band of Stability

N/Z as Z

1.3n:1p

1.2n:1p

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1n:1p

Ratio N/Z = 1

As Z , #N > Z and

e emitters

1.1n:1p

Each isotope is a dot


Up to Z = 20

1n:1p

e+ emitters

Jespersen/Brady/Hyslop

By Z = 82, N/Z ~1.5


N = # neutrons
Z = # protons

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How To Predict if Nuclei is Stable


1) Atomic Mass = weighted average of masses of
naturally occurring isotopes, i.e. most stable ones
2) Compare Atomic mass of element to A (atomic
mass number) of given isotope and see if it is
more or less
At. Mass > A
too light to be stable
too heavy to be stable
At. Mass < A
Ex.
At. Mass
180Os
190.2
135I

Conclusion
Too light, n poor

Pe

Too heavy, n Rich


126.9
Final Note:
All nuclei with Z > 83 are radioactive
Jespersen/Brady/Hyslop

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More Patterns of Stability


If we look at stable and unstable nuclei, other
patterns emerge
283 stable nuclides (out of several thousand known
nuclides)
If we look at which have even and odd Z and N;
patterns emerge
Z

Pe

even even
even odd
odd even
odd odd

# stable
nuclides
165
56
53
9

Jespersen/Brady/Hyslop

2H, 6Li, 10B, 14N

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More Patterns of Stability


Clearly NOT random: even must imply

greater stability

Not too surprising

Same is true of electrons in molecules

Pe

Most molecules have an even number of


electrons, as electrons pair up in orbitals
Odd e molecules, radicals, are very
unstable, i.e. very reactive!!

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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Magic Numbers

Look at binding energies, see certain


numbers of protons and neutrons result in

special stability

Pe

Called Magic Numbers


1n and 1p in separate shells
Magic numbers (for both 1n and 1p) are
2, 8, 20, 28, 50, 82, 126
For e pattern of stability is:
2, 10, 18, 36, 54, 86(Noble gases)

Jespersen/Brady/Hyslop

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Magic Numbers

Special stability of Noble Gases due to


closed shells of occupied orbitals
Structure of nucleus can also be
understood in terms of shell structure
With filled shells of 1n and 1p having added
stability

Pe

At some point adding more 1n to higher


energy neutron shells decreases stability
of nuclei with too high n/p ratio

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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Your Turn!

Isotopes above the band of stability are more


likely to:

Pe

A. emit alpha particles


B. emit gamma rays
C. capture electrons
D. emit beta particles

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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Radioactive Nuclei Found in Nature


Non-naturally occurring elements (man-made
unstable) are denoted by having atomic mass in
parentheses
All nuclei with Z > 83 are radioactive
Yet some elements with Z between 83 and 92 occur
naturally
Atomic weight is NOT in parentheses

How can this be?

Pe

There are 3 heavy nuclei, which have very long halflives


Long enough to have survived for billions of years

Each parent of natural decay chain


Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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Decay Chains

half-life () = 4.5 billion years


emitter
Daughter 234Th is also radioactive
emitter
Half-life much shorter

Long sequence of emissions, and

Pe

Recall that emission changes A by 4, while


emission A = 0
Result: every member of chain has
A = (4n + 2)
where n = some simple integer
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

55

238U
92

3m
214Pb
82

234Th
90

5109 y

218Po
84

Decay Chain

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238Uranium

4d

222Rn
86

27 m

214Bi
83

25 d

2103 y
,

20 m

Pe

206Pb
82

Jespersen/Brady/Hyslop

234Pa
91

226Ra
88

214Po
84

138 d

7 hr

8104 y

234U
92

5.7105 y
230Th
90

210Pb
82
4
1.610 s
, 22 y

210Po
84

5d

210Bi
83

A stable
isotope

Chemistry: The Molecular Nature of Matter, 6E

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Pe

Jespersen/Brady/Hyslop

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Decay Chains

Final stable member of sequence is 206Pb


Some intermediate nuclides have reasonably
short half-lives
Still found in nature because they are constantly
being replenished by decay of nuclei further up
chain

Pe

Uranium-containing minerals (pitchblende is


most famous) contain many radioactive
elements

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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Your Turn!

When the reaction, 22286 Rn


the particle emitted is:

218
84

Po +

n
m

,X occurs,

Pe

A. an alpha particle
B. a beta particle
C. an electron
D. a gamma ray

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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Transmutation

Change of one isotope for another


Caused by

1. Radioactive decay
2. Bombardment of nuclei with high energy particles

particles from natural emitters


Neutrons from atomic reactors
Protons made by stripping electrons for hydrogen

Pe

Protons and particles can be accelerated in


electrical field to give higher E
Mass and energy of bombarding particle enter target
nucleus to form compound nucleus

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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Processes

NON-SPONTANEOUS Nuclear
Fusion

Occurs in starsright now


How elements formed
12
4
16
2
1
3
C
+
He

O
+

H
+
H

6
2
8
1
1
2 He +

C + 11p

12
6

N +

13
7

Induced Fission

Mo + 01n

98
42

Mo +

99
42

Pe

Bombard heavy nuclei with neutron

U + 01n

235
92

Ba +

142
56

Jespersen/Brady/Hyslop

Kr + 2 01n

92
36

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Compound Nucleus

Designated with *
High energy due to velocity of incoming particle
Energy quickly redistributed among nucleons, but
usually unstable
To get rid of excess energy, nucleus ejects
something
Neutron
Proton
Electron
Gamma radiation

Pe

Decay leaves new nucleus different


from original
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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4
2 He

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Ex. Transmutation

14
7N

Pe

Bombard- Target
ing particle nucleus

18
9F

Compound
nucleus

Jespersen/Brady/Hyslop

17
8O

1
1p

New
High
nucleus energy
particle

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Transmutation

Can synthesize given nucleus in many ways:


4
2 He
1
1p
2
1H

23
11 Na
26
12 Mg

25
12 Mg

27
13 Al
27
13 Al

27
13 Al

Pe

Once formed, compound nucleus has no


memory of how it was made
Only knows how much energy it has

Jespersen/Brady/Hyslop

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Transmutation

Decay pathway depends on how much energy

26
12 Mg

26
1
13 Al + 0 n
25
1
12 Mg + 0 n

23
11 Na

0
0

1
1p

1
1p

4
2 He

Pe

27
13 Al

27
13 Al

Jespersen/Brady/Hyslop

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Transmutation

Used to synthesize new isotopes


> 900 total
Most not on band of stability

All elements above 93 (neptunium) are man


made
Includes Actinides above 93 + 104 112 + 114

Heavier elements made by colliding two


larger nuclei

Pe

Also known as fusion


62
28 Ni

208
82 Pb

270

Ds
110

Jespersen/Brady/Hyslop

269
110 Ds

1
0n

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Your Turn!

What would be the element produced from the


192
59
fusion of 27 Co with 76 Os ? The species would
be in a high energy state and in time would
undergo decay to other species.

Pe

A. No
B. Lr
C. U
D. Hs

Jespersen/Brady/Hyslop

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Measuring Radioactive Decay


Atomic radiation = ionizing radiation
Creates ions by knocking off electrons

Geiger Counter

Pe

Detects and radiation with enough E to


penetrate window
Inside tube, gas at low P, form ions when radiation
enters
Ions cause current to flow
Amount of current relates to amount of radiation

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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Measuring Radioactive Decay


Scintillation Counter

Surface covered with chemical


Emits tiny flash of light when hit by radiation
Emission magnified electronically and counted

Film Dosimeters

Pe

Piece of photographic film


Darkens when exposed to radiation
How dark depends on how much radiation exposure
over time
Too much exposure, person using must be
reassigned to other work
Jespersen/Brady/Hyslop

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Activity

Number of disintegrations per second


Used to characterize radioactive material

A = kN

k = 1st order decay constant in terms of number of

nuclei rate than concentration


N = number of radioactive nuclides

Pe

N
A=
= kN
t
Law of radioactive decay

Radioactive decay is 1st order kinetics process


Jespersen/Brady/Hyslop

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Units of Activity

SI unit

Bequerel (Bq)

1 disintegration per second (dps)


1 liter of air has ~ 0.04 Bq due to

14C

in CO2

Older unit

Curie (Ci)

Pe

3.7 x 1010 dps = 3.7 x 1010 Bq


Activity in 1.0 g 226Ra = 1 Ci

Jespersen/Brady/Hyslop

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Half-Life

Time it takes for number of nuclides present at


time t, Nt , to fall to half of its value.
ln 2 0.693
t1 =
=
2

Half-lives are used to characterize nuclides


If you know half-life:

Pe

Can use to compute k


Can also calculate A of known mass of radioisotope

Jespersen/Brady/Hyslop

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Ex. 3

What is the activity of 1.0 g of strontium-90?


The half-life = 28.1 years
Step 1. Convert t to seconds
365 day 24 hr 60 min 60 s
28.1 yr

1 yr
1 day
1 hr
1 min
= 8.86 10 8 s

Step 2. Convert t to k
=

Pe

k =

ln 2

t 12

0.693

8.86 10 s

Jespersen/Brady/Hyslop

= 7.82 10

10

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Ex. 3 (cont)

Step 3. Convert g

90Sr

to number of atoms (N)

1 mol Sr 6.02 10 23 atoms Sr


1.0 g Sr

90 g Sr
1 mol Sr
= 6.69 10 21 atoms Sr

Step 4. Calculate Activity = kN

A = 7.82 10 10 s 1 6.69 10 21 atoms Sr

Pe

A = 5.23 1012 atoms Sr/s 1 disintegration/atom


A = 5.23 1012 dps or 5.23 1012 Bq

Jespersen/Brady/Hyslop

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Ex. 4

3H, tritium, is a emitter with a half-life


t = 12.26 yrs. MW = 3.016 g/mol. How
many grams of 3H are in a 0.5 mCi sample?
Step 1. Convert half-life to s as Ci is in
disintegrations per second (dps)
12

365.25d
= (12.26yr )
yr

24hr 3600s
8

= 3.87 10 s

d hr

Step 2. Convert t to k

Pe

ln 2

k =

t1

ln 2

3.87 10 s

Jespersen/Brady/Hyslop

= 1.79 10

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Ex. 4 (cont)

Step 3. Convert Ci to dps


1Ci
A = 0.5mCi
1000mCi

10

3
.
7
10
dps

7
= 1.85 10 dps

Ci

Step 4. Calculate g 3H to get this activity

A 1.85 10 7 dps
16
= 1.03 10 atoms
N = =

9
1
k 1.79 10 s
Step 5. Convert atoms to g
3.016 g

23
6.022 10 atoms / mole mol

Pe

3
1H =

1.03 1016 atoms

= 5.2 108 g
Jespersen/Brady/Hyslop

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Exposure Units

Not all materials equally absorb radiation, thus


activity doesnt describe effect of exposure
1 gray (Gy) = 1 J absorbed energy/kg material
SI unit of absorbed radiation
1 rad = absorption of 102 J/ kilogram of tissue
Older unit
1 Gy = 100 rad

Pe

These units dont take into account type of


radiation

Jespersen/Brady/Hyslop

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Exposure Units

Sieverts (Sv)
SI unit of dose equivalent, H

Depends on amount and type of radiation as well


as type of tissue absorbing it
H=DQN

H = dose in Sv
D = dose in Gy
Q = radiation properties
N = other factors

Pe

Rem = older unit

1Rem = 102 Sv
Still used in medicine
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

78

Exposure to Radiation

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Typically X-ray = 0.007rem or 7mrem


0.3 rem/week is maximum safe exposure set by
US govt.
25 rem (0.25 Sv): Causes noticeable changes in
human blood
100 rem (1 Sv):
Radiation sickness starts to develop

200 rem (2 Sv):

Severe radiation sickness

400 rem (4 Sv):

Pe

50% die in 60 days


Level of exposure or workers at Chernobyl when steam
explosion tore apart reactor

600 rem (6 Sv): lethal dose to any human


Jespersen/Brady/Hyslop

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Your Turn!

Workers cleaning up the Fukushima reactors were


exposed to as much as 400 mSv units of radiation per
hour. How many rems of exposure does this
correspond to?

Pe

A. 4000 rem
B. 400 rem
C. 40 rem
D. 4 rem

100 mrem 1 rem


= 40 rem
400 mSv

mSv 1000 mrem

Jespersen/Brady/Hyslop

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Why is Radiation Harmful?

Not heat energy

Ability of ionizing radiation to form unstable ions


or neutral species with odd (unpaired) electrons

Free radicals

Pe

Chemically very reactive


Can set off other reactions
Do great damage in cell
radiation
H O H
H O
H O H

Jespersen/Brady/Hyslop

H+

0
e
-1

O H

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Which Types are Most Harmful?


High energy gamma () radiation and X-rays
Massless
High velocity
Penetrate everything but very dense materials,
such as lead

Which type is least harmful?


Alpha () particles

Pe

Most massive
Quickly slow after leaving nucleus
Dont penetrate skin
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

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Background Radiation

Presence of natural radionuclides means we cant


escape exposure to some background radiation
Cosmic rays (from sun) hit earth

Turn 14N 13C


13C emits particles
Incorporated into food chain from CO2 via photosynthesis

Radiation from soil and building stone

From radionuclides native to Earths crust


Top 40 cm of soil hold 1 g radium () /sq kilometer
40K emit particles

Pe

Total average exposure 360 mrem/year


82% natural radiation
Jespersen/Brady/Hyslop

18 % man made

Chemistry: The Molecular Nature of Matter, 6E

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Radiation Intensity

Intensity of radiation varies with distance


from the source
Farther from emitter, lower intensity of
exposure
Relationship is governed by Inverse
Square Law, where:

Pe

I is intensity and
d is distance from source

I1 d22
=
I2 d12

Jespersen/Brady/Hyslop

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Ex. 5

If the activity of a sample is 10 units at 5


meters from the source, what is it at 10 m?
2

I1 d1
10units (5m )
I2 =
=
= 2.5units
2
2
d2
(10m )
What distance is needed to reduce 1 unit at 1
yd to the 0.05 units?

Pe

d2 =

I1 d12
1 unit (1yd ) 2
=
I2
0.05 units
= 20yd 2 = 4.8yd

Jespersen/Brady/Hyslop

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Your Turn!

Pe

How far away from a radioactive source producing 40


rem/hr at a distance of 10 m would you need to be to
reduce your exposure to 0.4 rem/hr?
A. 32 m
B. 100 m
C. 200 m
D. 1000 m

d2 =

( 40 rem )(10 m)

Jespersen/Brady/Hyslop

0.4 rem

= 100 m

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Radioactive DecayKinetics
Spontaneous decay of any nuclide follows

first order kinetics

May be complicated by decay of daughter nuclide


For now consider single step decay processes

Rate of reaction for 1st order process


A products
In nuclear reaction, consider rate based on
number of nuclei N present

Pe

dN
= kN
Rate of Reaction =
dt
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

87

Pe

Plot ln N (y axis) versus t (x


axis)
Yields straight lineindicative of
1st order kinetics
Plot of N vs. time gives an
exponential decay.
kt

N = number of nuclei present at


time t
No = number of nuclei present at t
=0

ln N

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The integrated form is:


ln N ln No = kt

Radioactive DecayKinetics

N = Noe

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

88

is used as a metabolic tracer in


hospitals. It has a half-life, = 8.07
days. How long before the activity falls to
1% of the initial value?
N

t
ln
2
= kt =
ln
N = N o e kt
No
12

131I

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Ex. 6

ln 2

Pe

t =

N
1 2 ln
No

1
(8.07 days ) ln

100

=
ln 2

t = 53.6 days
Jespersen/Brady/Hyslop

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Your Turn!

How many hours will it take a radioisotope with


a half-life of 10.0 hours to drop to 12.5% of its
original activity?

Pe

A. 30.0 hrs
B. 20.0 hrs
C. 40.0 hrs
D. 63.2 hrs
12.5% of original activity is 3 half-lives or
30.0 hrs.
Jespersen/Brady/Hyslop

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Radioisotope Dating

How old is an object?

Fields Geology, Archeology, and Anthropology

Pe

Nature provides us with natural clocks or


stopwatches
A) Radiocarbon Dating (Willard Libby
Nobel Prize in 1960)
Cosmic rays (from space) enter atmosphere
Some react with N in atmosphere forming
radioisotope 14C
emitter with t = 5730 yr
14
7N

1
0n

Jespersen/Brady/Hyslop

14
6C

1
1H

Chemistry: The Molecular Nature of Matter, 6E

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Dating

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14C

becomes incorporated into atmospheric


CO2 in very small quantities

14C

14C/12C

ratio in air is slightly greater than Earths


crust because of ongoing enrichment

Living organisms breath, eat, etc

14C/12C

equilibrate with atmosphere

Radioactive 14C is uniformly distributed


around globe

Pe

Tested experimentally
Checked vs. counting tree rings, etc.
For precise work, use correction based on
alternate methods
Jespersen/Brady/Hyslop

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14C

HOW? Freshly cut wood samples have


~15.3 cpm per gram of total carbon

cpm = counts per minute


Ao = 15.3 cpm/g total C

Assumption: Ao was always 15.3 cpm,


i.e. cosmic radiation is constant
When organism dies

Pe

it stops eating, breathing, etc


14C starts to decrease

Jespersen/Brady/Hyslop

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14C

Wooden implement in Egyptian tomb (~3000


BC)
Have about half activity of fresh sample
~5000 years have elapsed

Method is applicable for objects


Few hundred to ~20,000 years

Beyond this

Activity of sample is very low


Experimental uncertainties too big

Pe

This method used for dating

1. Charcoal in cave paintings


2. Linen wraps on Dead Sea scrolls
Jespersen/Brady/Hyslop

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Ex. 7

Geologists examine shells found in cliffs.


Shells are CaCO3 and are made by living
organisms. The activity of the shells is
found to be 6.24 cpm/g total C. How old
is the cliff formation?
Can use N/No and
A
t ln 2
= kt =
ln
A/Ao interchangeably
Ao
t 12

Pe

as
A = kN
A = 6.24 cpm/g total C
Ao = 15.3 cpm/g total C Since ratio, k cancels

t = 5730 yr

Jespersen/Brady/Hyslop

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Ex. 7 (continued)

A t ln 2
ln
=
12
Ao

Rearranging and solving for t


A
t 1 2 ln
Ao
t =
ln 2

Pe

6.24 cpm

(5730 yr ) ln
15.3 cpm

t =
ln 2

t = 7414 yr

Jespersen/Brady/Hyslop

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B) Other Isotopes Provide Natural


Clocks
Minerals (moon rocks) dated using isotopes
with much longer half-lives
9 yr
40
0
40
t
=
1.27
x
10
+ 18 Ar

19 K + 1 e
40

K
Compare 40
ratios in rock
Ar
238
92U

206
82 Pb

+ 8 24He + 6

0
1

t = 4.5 x 109 yr

Pe

Rock with no other source of Pb can be


dated using 238U ratios
206

Pb

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Ex. 8

A sample of rock is found to contain 0.232g


of 206Pb and 1.605g 238U. Assuming that all
the 206Pb now present came from the decay
of 238U, calculate the time since the
solidification of this rock.
Step 1. Mass of 238U that decayed =

U
0.232 g
206
Pb
238

206

Pb

Pe

238 g / mol

206 g / mol

= 0.268 g 238U decayed


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Ex. 8 (continued)

Step 2. Mass of 238U in rock initially (t = 0)


No = 1.605 g + 0.268 g = 1.873 g
ln 2 * t
1.873
ln
=
1.605 4.5 10 9 yr

N o ln 2 * t
ln
=
t 12
N

0.1544 =

0.693147 * t
9

4.5 10 yr

Pe

0.1544 4.5 10 9 yr
t =
0.693147
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t = 1.0 x 109 yr

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Your Turn!

A wooden bowl fragment found at an old camp site


thought to be approximately 11,000 years old was
submitted for carbon-14 analysis. The sample was
found to have 4.67 cpm/g total C. What is the actual
age of the sample?
4260 yrs
3347 yrs
9810 yrs
2523 yrs
t = {5730 yrs x ln(4.67/15.3)}/ln2 = 9810 yrs

Pe

A.
B.
C.
D.

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Fission

Induce by bombarding
unstable nucleus with
a slow neutron
Nuclear chain reaction
Neutrons generated
keep going

Pe

With small mass of


235U reaction
continues, but easily
controlled
Some neutrons are
lost to environment

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Fission

Critical mass

Too much 235U in one


place
Too many neutrons
absorbed
Too few lost
Uncontrollable fission
Leads to explosion

Pe

Use control rods to


absorb excess
neutrons and keep
reaction from
going critical
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Nuclear Reactor

No chance of nuclear explosion

Critical mass requires pure 235U


Reactor rods 2 4% 235U rest non-fissionable

238U

Core meltdown possible

If heat of fission not carried away by cooling water


Or

Explosion possible

Pe

High heat of fission splits H2O into H and O, which


recombine very exothermically and cause explosion
What happened at Chernobyl

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Nuclear Reactors

Could it happen at U.S. reactors?

Extremely unlikely
Chernobyl only single containment system
U.S. has all double containment systems
U.S. extra backup systems - both computer and
mechanical that would prevent

Pe

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Nuclear Reactor

Use heat from nuclear reaction to heat steam turbine


Use to generate electricity
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Your Turn!

Which of the following fission reactions is


balanced?
A.

235
92

U + 01 n

B.

235
92

U + 01 n

142
56

Ba +

92
36

Kr + 01 n

235
92

U + 01 n

141
56

Ba +

92
36

Kr + 2 01 n

Pe

C.

142
56

D.

235
92

U + 01 n
Jespersen/Brady/Hyslop

Ba +

142
55

92
36

Cs +

Kr + 2 01 n

92
36

Kr + 2 01 n

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Nuclear Fusion

Occurs when light nuclei join to form heavier


nucleus
On a mass basis, fusion yields more than five
times as much energy as fission
Source of the energy released in the explosion
of a H-bomb
The energy needed to trigger the fusion is provided
by the explosion of a fission bomb

Pe

Source of energy in stars

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Thermonuclear Fusion

Uses high temperatures to overcome electrostatic


repulsions between nuclei
T required are >100 million C
Atoms want to fuse stripped of electrons
High initial energy cost

Plasma

Electrically neutral, gaseous mixture of nuclei and electrons

Make plasma very dense (>200g/cm3


Brings nuclei within 2 fm = 21015 m
Pressures = several billion atms

Pe

Not there yet, major problem

Containment of high temperature and pressures


Magnetic field current approach
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