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Chapter 26

Nuclear Chemistry

1
Chapter Goals
1. The Nucleus
2. Neutron-Proton Ratio and Nuclear Stability
3. Nuclear Stability and Binding Energy
4. Radioactive Decay
5. Equations for Nuclear Reactions
6. Neutron-Rich Nuclei (Above the Band of Stability)
7. Neutron-Poor Nuclei (Below the Band of Stability)
8. Nuclei with Atomic Number Greater than 83
9. Detection of Radiation

2
Chapter Goals

10. Rates of Decay and Half-Life


11. Disintegration Series
12. Uses of Radionuclides
13. Artificial Transmutations of Elements
14. Nuclear Fission
15. Nuclear Fission Reactors
16. Nuclear Fusion
3
Comparison Of Chemical
and Nuclear Reactions
Nuclear Reactions Chemical Reactions
1 Elements may be 1 No new elements can
converted from one be produced, only new
element to another. chemical compounds.
2 Particles within the 2 Usually only the outer
nucleus, such as most electrons
protons and neutrons, participate in reactions.
are involved in
reactions.
4
Comparison Of Chemical
and Nuclear Reactions
Nuclear Reactions Chemical Reactions
3 Release or absorb 3 Release or absorb
immense amounts of much smaller amounts
energy, typically 1000 of energy.
times more. 4 Rates of reaction
4 Rates of reaction are depend on factors such
not influenced by as concentration,
external factors. pressure, temperature,
and catalysts.
5
Beginning of Nuclear Science
In 1896, Henri Becquerel accidentally
discovered radioactivity in U salts.
In 1898, Marie and Pierre Curie discovered two
new radioactive elements in U mine residue.
Po and Ra
In 1898, Ernest Rutherford discovered that
radioactivity has two distinct forms.
and radiation

6
Fundamental Particles
of Matter
PARTICLE MASS (amu) CHARGE

Electron 0.0005458 1-
(e-)
Proton 1.0073 1+
(p or p+)
Neutron 1.0087 none
0
(n or n )

7
The Nucleus
The nucleus consists of protons and neutrons in a very
small volume.
Protons and neutrons are made of other

fundamental particles called quarks.


Nuclei have a diameter of approximately 10-12 cm
Nuclei have a density of approximately 2 x 1014 g/cm3.
The strong nuclear force binds the nucleus together at
extremely short distances of 10-13 cm

8
Neutron-Proton Ratio
and Nuclear Stability
Terminology used in nuclear chemistry.
1. Nuclides denotes different nuclei.
2. Isotopes are nuclei that have the same number of
protons but different neutron numbers.
Isotopes are the same element.

Experimentally, it can be shown that nuclei have a


preference for even numbers of protons and neutrons
The next table is all of the nonradioactive nuclides broken
into various combinations of protons and neutrons.

9
Radioactive Decay
Nucleiwhoseneutrontoprotonratioliesoutside
thebeltofstabilityexperiencespontaneous
radioactivedecay.
Decaytypedependsonwherethenucleiis
positionedrelativetothebandofstability.
Radioactiveparticlesareemittedwithdifferent
kineticenergies.
Energychangeisrelatedtothechangeinbindingenergyfrom
reactanttoproducts.

10
Radioactive Decay

11
Neutron-Proton Ratio
and Nuclear Stability

Proton Number Neutron Number Number of Nuclides


Even Even 157
Even Odd 52
Odd Even 50
Odd Odd 4

12
Neutron-Proton Ratio
and Nuclear Stability
Special stability is associated with
certain proton and neutron numbers
due to shell effects in nuclei similar to the
s, p, d, and f shells in atoms
These proton and neutron numbers are
called Magic Numbers.
Magic numbers are:
2 8 20 28 50 82 126
13
Neutron-Proton Ratio
and Nuclear Stability
Example nuclides with magic numbers of
nucleons includes:
4
2 He 2 a doubly magic nucleus
16
8 O8 a doubly magic nucleus
40
20 Ca 20 a doubly magic nucleus
48
20 Ca 28 a doubly magic nucleus
120
50 Sn 70 a singly magic nucleus
208
82 Pb126 a doubly magic nucleus 14
Nuclear Stability and
Binding Energy
The mass deficiency or mass defect of a nucleus is
determined in this fashion.


m sum of masses of all p , n and e - actual mass of atom
The mass defect is the mass of the nuclear
particles that has been used to bind the
nucleus in the nuclear binding energy or
strong nuclear force.

15
Nuclear Stability and
Binding Energy
Due to the Einstein relationship, we can calculate the nuclear
binding energy for a nucleus.

E mc 2
E m c 2
or
Binding Energy m c 2
Nuclear binding energy may be expressed
in many different units ( KJ/mole, KJ/gram
and MeV/ nucleon
1 megaelectron volt (MeV)= 1.60 x 10-13J
16
1 Joule (J) = 1 kg.m2/s2
Nuclear Stability and
Binding Energy
Example 26-1: Calculate the mass
deficiency for 39K. The actual mass of
39K is 39.32197 amu per atom.

39
K has 19 protons, 20 neutrons and 19 electrons
1 proton has a mass of 1.0073 amu
1 neutron has a mass of 1.0087 amu
1 electron has a mass of 0.0005458 amu
17
Nuclear Stability and
Binding Energy
Example 26-1: Calculate the mass
deficiency for 39K. The actual mass of 39K is
39.32197 amu per atom.
Thesum
The sumofofthe
themasses
massesofoftheprotons, neutrons,
protons, neutrons,and electrons
and electronsis is:
19
191.0073 amu 20 1.0087 amu 19 0.0005458
1.0073 amu amu
0.0005458 amu
19.1387 amu 20.1740 amu 0.0104 amu
39.32307 amu
m 39.32307 amu - 39.32197 amu
m 0.00110 amu
18
Nuclear Stability and
Binding Energy
Example 26-2: Calculate the nuclear
binding energy of 39K in J/mol of K
atoms. 1 J = 1 kg m2/s2.
m = 0.00110 amu
atom 6.022 10 23 atoms
mol

6.624 10 20 amu
mol 1.66110 24 g
amu

19
Nuclear Stability and
Binding Energy
Example 26-2: Calculate the nuclear
binding energy of 39K in J/mol of K
atoms. 1 J = 1 kg m2/s2.

m = 0.00110 atom 6.022 10
amu 23 atoms
mol
6.624 10 20 amu
mol 1.66110 24 g
amu
6 kg
0.00110 g
mol 1.10 10 mol

20
Nuclear Stability and
Binding Energy
Example 26-2: Calculate the nuclear
binding energy of 39K in J/mol of K
atoms. 1 J = 1 kg m2/s2.
2
E = mc 110
. 10 6 kg
8m 2
mol 3.00 10 s

110
. 10 6 kg
mol 9.00 10 16 m2
s2
10 kg m2 10 J
9.90 10 s2 mol
9.90 10 mol
21
EquationsforNuclear
Reactions
Twoconservationprinciplesholdfor
nuclearreactionequations.
1. Thesumofthemassnumbersofthereactantsequals
thesumofthemassnumbersoftheproducts.
2. Thesumoftheatomicnumbersofthereactants
equalsthesumoftheatomicnumbersoftheproducts.

22
EquationsforNuclear
Reactions
Forthegeneralreaction:
M1
Z1 Q R Y
M2
Z2
M3
Z3
Thetwoconservationprinciplesdemand
1. M1 = M2+M3
and
2. Z1 = Z2+Z3
WheretheM'saremassnumbers,
AndtheZ'sareatomicnumbers. 23
NeutronRichNuclei(Abovethe
BandofStability)
Thesenucleihavetoohigharatioofneutronsto
protons.
Decaysmustlowerthisratioandinclude:
betaemission

neutronemission

24
NeutronRichNuclei(Abovethe
BandofStability)
BETAEMISSION
Betaemissionisassociatedwiththeconversionofaneutrontoa
proton;
Betaemissionsimultaneouslydecreasesthenumberofneutrons
(byone)andincreasesthenumberofprotons(byone).
Efficientlychangestheneutrontoprotonratio.

1
Examplesofbetaemission:
1 0
0 n1 p 1
14
6C
14
7 N 0
+-1
226
88 Ra 226
89 Ac +-10 25
NeutronRichNuclei(Abovethe
BandofStability)
NEUTRONEMISSION
Neutronemissiondoesnotchangetheatomicnumber,butit
decreasesthenumberofneutrons.
Theproductisotopeislessmassivebythemassof1neutron.

Examplesofneutronemission

17
7 N N+ n
16
7
1
0
137
53 I I+ n
136
53
1
0

26
NeutronPoorNuclei(Belowthe
BandofStability)
Thesenuclideshavetoolowaratioof
neutronstoprotons.
Nuclearradioactivedecaysmustraisethis
ratio
Thepossibledecaysinclude:
1. electroncapture(Kcapture)
2. positronemission

27
NeutronPoorNuclei(Belowthe
BandofStability)
ELECTRONCAPTURE

Electroncaptureinvolvesthecaptureofanelectroninthe
lowestenergylevelintheatombythenucleus.
conversionofaprotontoaneutron

1
1 p e n 0
-1
1
0
37
18 Ar e Cl 0
-1
37
17
28
NeutronPoorNuclei(Belowthe
BandofStability)
POSITRONEMISSION
Apositronhasthemassofanelectronbuthasapositivecharge.
Thesymbolis0+1e.

Positronemissionisassociatedwiththeconversionofaproton
intoaneutron.

p
11 p nn
ee
0
0 11
1 1
1 00
1 1 0
39
K e 0 39
Ar
39
19
19 K 01 e 0
1
18 Ar 39
18

8 O 1 e 7 N
15 15 29
NucleiwithAtomicNumber
Greaterthan83
Alphaemissionoccursforsomenuclides,
especiallyheavierones.
Alpha()particlesareheliumnuclei,
4 He,containingtwoprotonsandtwo
2
neutrons.
Alphaemissionincreasestheneutronto
protonratio.
204
82 Pb Hg He200
80
4
2 30
NucleiwithAtomicNumber
Greaterthan83
Allnuclideshavingatomicnumbers
greaterthan83arebeyondthebeltof
stabilityandareradioactive.
Manyoftheseisotopesdecaybyemitting
alphaparticles.

238
92 U Th He
234
90
4
2
31
NucleiwithAtomicNumber
Greaterthan83
Thetransuraniumelements(Z>92)also
decaybynuclearfissioninwhichthe
heavynuclidesplitsintonuclidesof
intermediatemassandneutrons.
252
98 Cf Ba
142
56
106
42 Mo 4 n
1
0

32
DetectionofRadiation
Presentradiationdetectionschemesdependonthe
factthatparticlesandradiationsemittedby
radioactivedecayareenergeticandsomecarry
charges.

1. PhotographicDetection
Radioactivityaffectsphotographicplatesorfilm
asdoesordinarylight.
Medicalanddentalxrayphotographsaremade
usingthistechnique.
33
DetectionofRadiation

2. FluorescenceDetection
Fluorescentsubstancesabsorbenergyfrom
highenergyraysandthenemitvisiblelight.
Ascintillationcounterisaninstrument
usingthisprinciple.

34
DetectionofRadiation
3. CloudChamberscontainairsaturated
withavapor.
Radioactivedecayparticlesemittedionize
theairmoleculesinthechamber.
Thevaporcondensesontheseions.
Thentheiontracksarephotographed.

35
DetectionofRadiation
4. GasIonizationCounters
Theionsproducedbyionizingradiationare
passedbetweenhighvoltageelectrodes
causingacurrenttoflowbetweenthe
electrodesandthecurrentisamplified.
Thisisthebasisofoperationofgas
ionizationcounterssuchastheGeiger
Muellercounter.

36
DetectionofRadiation
Schematic of Geiger Counter

37
RatesofDecayandHalfLife
Theratesofallradioactivedecaysare
independentoftemperatureandobeyfirst
orderkinetics.
Thesamerelationshipsdevelopedin
Chapter16applyhereaswell.
Rate of decay k A or
A0
ln akt
A 38
RatesofDecayandHalfLife
Forcountingradioactivedecaythe
relationshipchangesjustslightly:

Rate of decay k A or
N0
ln akt
N

39
RatesofDecayandHalfLife
Thehalflife,t1/2,isrelatedtotherate
constantbythesimplerelationship:

ln 2 0.693
t 12
ak ak

40
RatesofDecayandHalfLife
Example263:Howmuch60Coremains15.0
yearsafteritisinitiallymade?60Cohasahalf
lifeof5.27years.
A0
ln a k t k t for this case
A A 1.0 (0.139)
A
ln
A0


k t
A 0.139 or 13.9% remains
A
e k t
A0

t 12
ln 2

0.693 A A0 ek t
A 1.0 e
ak ak
0.693 0.693 0.132 y -1 15.0 y
k
t 12 5.27 y
k 0.132 y -1 A 1.0 e 1.97 41
Disintegration Series
Somenuclidesaresofarawayfromthebeltofstability,
thatittakesmanynucleardisintegrations(aseriesofthem)
toattainnuclearstability.
Thedecayingnuclideiscalledparentnuclide.
Theproductnuclideisthedaughter.
Example:
238Udecaysbyalphaemissionto234Thinthefirststepofone
series.234Thsubsequentlyemitsabetapartcilestoproduce 234Pa
inthesecondstep.Theseriescanbesummarizedinthenext
figure.

42
Disintegration Series

43
UsesofRadionuclides
RadioactiveDating
Radiocarbondatingcanbeusedto
estimatetheagesofitemsoforganic
origin.
14Cisproducedcontinuouslyintheupper

atmospherebythebombardmentof14Nby
cosmicrayneutrons:

14
N n C p
1
0
14
6
1
1 44
UsesofRadionuclides
14CatomsreactwithO2toformCO2
TheCO2thenisincorporatedintoplantlife
byphotosynthesis.
Aftertheorganismdiesthe14Ccontent
decreasesviaradioactivedecay
The14Chalflifeis5730years.
14
6 C N 14
7
0
-1 45
UsesofRadionuclides
Thepotassiumargonanduraniumlead
methodsareusedfordatingolderobjects.
Potassiumargonmethodreliesonthe
electroncapturedecayof40Kto40Ar

40
19 K Ar e
40
18
0
1

t 12 1.3 10 y 9

46
UsesofRadionuclides
Theuraniumleadmethodreliesonthe
alphadecayof238Uto234Th.

238
92 U 234
90 Th He 4
2

t 12 4.5 10 y 9

47
UsesofRadionuclides
Example264:Estimatetheageofan
objectwhose14Cactivityisonly55%that
oflivingwood.
1. Determinetherateconstantfor14C.

0.693 0.693
t 12
ak k
0.693 0.693 4 1
k 1.2110 y
t 12 5730 y 48
UsesofRadionuclides
2. Determinetheageoftheobject.

0.598
ln 1.21
A 0
a kt10
4 1
k ty
in thist case
A
0.598
ln
100% t 1.2110

4 4 y
11
t
55% 1.21 10 y
ln 1.82
t 4940
1.21y10 4 y 1 t

49
ArtificialTransmutations
ofElements
Bombardmentofanuclidewithanuclearparticlecanmakeanunstablecompoundnucleus
thatdecaystoanewnuclidebyemissionofadifferentparticle.
Therulesforbalancingequationsfornuclearreactionswhichwerepresentedinthesectionon
radioactivitystillhold.

50
ArtificialTransmutations
ofElements
BombardmentwithPositiveIons
Ifthebombardingparticleispositivelycharged,itmustbeacceleratedwith
sufficientenergytoovercomethecoulombrepulsionofthepositivenucleus
bombardingparticlespenetratethenucleus
Particleacceleratorssuchas cyclotronsor linearacceleratorsareusedfor
this.

51
ArtificialTransmutations
ofElements
Example reactions are:
96
42 Mo H Tc n
2
1
97
43
1
0

52
ArtificialTransmutations
ofElements

96
42 Mo H Tc n
2
1
97
43
1
0
209
83 Bi He 3 n
4
2
1
0
210
85 At

53
ArtificialTransmutations
ofElements
96
42 Mo H Tc n
2
1
97
43
1
0
209
83 Bi He 3 n
4
2
1
0
210
85 At
230
90 Th H 3 n
1
1
1
0 ?

54
ArtificialTransmutations
ofElements

96
42 Mo H Tc n
2
1
97
43
1
0
209
83 Bi He 3 n
4
2
1
0
210
85 At
230
90 Th H 3 n
1
1
1
0
228
91 Pa
55
ArtificialTransmutations
ofElements
NeutronBombardment
Becauseneutronshavenocharge,thereisnocoulombrepulsiontotheirnuclearpenetration,so
theydonothavetobeaccelerated.
Nuclearreactorsareoftenusedasneutronsources.

56
ArtificialTransmutations
ofElements
Neutronswithlargekineticenergyarecalledfastneutrons.
Slowneutrons("thermalneutrons")havehadtheirexcessenergydecreasedbycollisionswithmoderators
Commonmoderatorsarehydrogen,deuterium,orthehydrogenatomsinparaffin.
Slowneutronsaremorelikelytobecapturedbytargetnuclei.

57
ArtificialTransmutations
ofElements

200
80 Hg n Hg n, reaction
1
0
201
80
0
0

58
ArtificialTransmutations
ofElements
200
80 Hg n
1
0 Hg n, reaction
201
80
0
0
6
3 Li n H He n, reaction
1
0
3
1
4
2

59
NuclearFission
Somenuclideswithatomicnumbersgreaterthan80are
abletoundergofission.
Thesenucleisplitintonucleiofintermediatemassesandemit
oneormoreneutrons.
Somefissionsarespontaneouswhileothersrequire
activationbyneutronbombardment.
Enormousamountsofenergyarereleasedinthese
fissions.
Someofthenumerouspossiblefissionpathsfor 235U(after
bombardmentbyaneutron)are:

60
NuclearFission
Fissionisenergeticallyfavorablefor
elementswithZgreaterthan80
Theproductnuclidesaremorestable(near
thehighpartofthenuclearbindingenergy
curve).

61
NuclearFission

62
NuclearFission

160
62 Sm Zn 4 n energy
72
30
1
0
146
57 La Br 3 n energy
87
35
1
0
235
92 U 01n 236
92
U 140
56 Ba 36
93
Kr 301 n energy
144
55 Cs Rb 2 n energy
90
37
1
0
144
54 Xe Sr 2 n energy
90
38
1
0

63
NuclearFissionReactors
Electricity can be generated from steam
heated by nuclear fission reactions.
Greatest danger of nuclear reactors is
core meltdown.
There have been two very serious
nuclear reactor accidents:
1. Three Mile Island in PA.
2. Chernobyl in the Ukraine.
64
NuclearFissionReactors
DescriptionofNuclearReactors
LightWaterReactorsusenormalwaterasthecoolant
andmoderator.
TypicalReactorFuelsare:
235 UO2
239 Pu
Moderatoristhematerialthatslowsneutronsfromfast
tothermal.
Commonlyusedmoderatorsaregraphite,water,heavywater.

65
NuclearFissionReactors
ControlRodsareusuallymadeofboronwhichisan
efficientneutronabsorber.
Controlrodsremoveneutronsandslowthechainreaction.
CoolingSystems
Thereactorcoremustbecooledtoremovetheheatfrom
thenuclearreactions.
Somepossiblecoolantsare:
waterbothnormalandheavy
helium
liquidsodium

66
NuclearFissionReactors
Shieldingprovidesworkersandpublic
withprotectionfromradiation.
Leadandconcretearecommonlyusedin
commercialreactors.

67
NuclearFissionReactors

68
NuclearFusion
Fusion, the merging of light nuclei to make
heavier nuclei, is favorable for very light atoms.
Extremely high energies or temperatures are
necessary to initiate fusion reactions.
The energy source for stars is fusion.
The fusion reaction in main sequence stars is:

2
1 H H He n energy
3
1
4
2
1
0
69
NuclearFusion

70
NuclearFusion
Fusion is the most energetic process in
nature.
Fusion has produced all of the chemical
elements beyond H and He up to Fe.
Fusion is a potential energy source for
humans.
Thermonuclear or hydrogen bombs
have been in existence since the
1950s.
71
NuclearFusion
Controlled nuclear fusion is a very real possibility.
Nuclear fusion must occur at temperatures of 10
million oC.
Fusion reactors must contain this temperature
and not melt!
Some fusion reactors exist around the world
However at present none can generate a sustainable
fusion reaction.
Potential energy source for the 21 st Century.

72
Synthesis Question
How are thermonuclear or fusion
reactors designed so that the hot
plasma, temperature of approximately
10 x 106 degrees, does not touch the
sides of the reactor? The reactor
would melt if the plasma were to touch
the sides.

73
Synthesis Question
Most fusion reactors use intense
magnetic fields to confine the hot
plasma in the center of the reactor
away from the walls.

74
Group Question
Stars are enormous thermonuclear
fusion reactors generating enormous
amounts of heat and energy. What
keeps stars from blowing themselves
apart? How do they remain stable for
millions and billions of years?

75
End of Chapter 26
Nuclear science has been one of the
driving forces of science in the 20th
Century.

76