Beruflich Dokumente
Kultur Dokumente
INTRODUCTION TO NUCLEAR
CHEMISTRY
20.1 RADIOACTIVITY
of billions of years. After about 30 billion years, the sample would be nearly gone.
Strontium-90, formed by nuclear reactions that occur in nuclear weapons testing
and nuclear power reactors, decays more rapidly. A sample of strontium-90 would
be nearly gone after several hundred years. In either case, it is impossible to know
when a particular nucleus will decay, although, as you will see in Section 20.4. pre-
cise information can be given about the rate of decay of any radioactive sample.
Nuclear Equations
You can write an equation for the nuclear reaction corresponding to the decay of
uranium-238 much as you would write an equation for a chemical reaction. You rep-
N l1chde symbols were jntro- resent the uranium-238 nucleus by the nuclide symbol 2~~U. <1 The radioactive
duced 10 Section 2.3. For decay of 2~~U by alpha-particle emission (loss of a iHe nucleus) is written
uranium-238, you write
2~~U _ 2~Th + iHe
m3SS number ---J:>. ::!38U
~lomlC nllmber --------. 9'2
The product. in addition to helium-4. is thorium-234. This is an example of a
nuclear equation, which is a symbolic representation of a nuclear reaction. Nor-
mally. only the nuclei are represented. It is not necessary to indicate the chemical
+ Luminescent
screen
~
\""1
FIGllRE 20.2 Uranium mineral
Separ;)tion of the radiation
from a radioactive material )
(uranium mineral). The radil1-
lion separates into J.lpha (al. ---------7L--...,~~=_-----'-,~ y r8Y
compound or the electron charges for any ions involved, because the chemical envi-
) ronment has no effect on nuclear processes.
Reactant and product nuclei are represented in nuclear equations by their
nuclide symbols Other particles are given the following symbols, in which the sub-
script equals the charge and the superscript equals the total number of protons and
neutrons in the particle (mass number):
Proton lH or ip
Neutron 60
Electron _~e or -?13
Positron ?e or ?f3
Gamma photon g1
The decay of a nucleus with the emission of an electron, _?e, is usually called beta
emission. and the emitted electron is sometimes labeled _? {3. A positron is a parti-
cle similar to an electron, having the same mass but a positive charge. A gamma
photon is a particle ofelectromagnetic radiation of short wavelength (about 1 pm,
or 10- 12 m) and high energy.
EXAMPLE 20"1
Writing a NlIdellrEquatioil .
write th~ nuckarequationfoc th~raPioactiyedecily pf radium-Z26 by alpha decaY to
givec~don'222, ,'\.iadiuin-n6 nucieu.eiltit$on~ alpha partjcl~, leaVing behind a
radbn-222nucl"U~.,:' .. . . . .
,- --
Exercise 20.1
PotassiumAO is a naturally occurring radioactive isotope. It decays to calcium-40 by
beta emission. When a potassiiJm-40 nucleus decays by beta emission, it emits one
beta p3,rticle and gives a calcium-40 nucleus. Write the nuclear equation for this decay.
remains cunstant, during 3 nuclear re3clioll. This means that (he sum of the super-
scripts (the mass numbers) for the reactants equals t.he sum of the superscripts for
'. )
20.1 RADIOACTIVITY
the products. For the equation in Example 20.1, the superscript for the reactant
nucleus is 226. For the products, the sum of the superscripts is 222 + 4 = 226.
Note that if all reactants and products but one are known in a nuclear equation,
839
the identity of that one nucleus or particle can be easily obtained. This is illustrated
in the next example.
EXAMPLE 20.2
Deducinga Prod\lct or Reactartt in a N\lc!ear Equation
Technetium-99 is a long"lived radioactive isotope of technetium. Each nucleus decaYs
by e,mitting one beta particle, What i.s th~prodllct nucleus?
1'!l()IILEM STRATEGY
FirSt write the nuclear eqoati()l1usi~g;'_SYIIlbb~,,~X, for th~unknow~:_nudicle or par-
j'
. tic.te~ Th~t,,',~olx~t~r A a~~ :Z-~sin~ _ ~et?lll:;~iJ1~ r~la}ions: (1) the. sum of the sub'-
scripts for the reacl~ntS eg~als ~suItiof !hesP\J~cripls forthe l"0duct" and (2) the
sP.P}Oit~~supe~soriptsf9rt-6d,'{(lc.ta,~is: equats~e_slllJlofttie. super$C'ripts: for: the
ptoducts. . . . . ..' .
SOLUTION .. .
'....'
Nuclear Stability
At first glance, the existence of several protons in the small space of a nucleus is
puzzling. Why wouldn't the protons be strongly repelled by their like electric
charges? The eXistence of stable nuclei with more than one proton is due to the
nuclear force. The nuclear force is a strong force of auractioll betweell nucleons
that acts ollly at very short distallces (abo III ]0- j j my. Beyond nuclear distances,
these nuclear forces become negligible. Therefore, two protons that are much far-
ther apart than 10- 15 m repel one another by their like electric charges. Inside the
nucleus, however, two protons are close enough together for the nuclear force
between them to be effective. This force. in a nucleus can more than compensate for
the repulsion of electric charges and thereby give a stable nucleus
840 C HAP TE R 20 NUCLEAR CHEMISTRY
The prolons and neutrons in a nucleus appearto have energy levels much as the
electrons in an atom have energy levels. The shell model of the nucleus is a
nuclear mode/Ill which protons and Ileutrons exist 111 levels, Or shells, analogous to
the shell structure that exists for electrolls ill all atOIl1. Recall that, in an atom, filled
shells of electrons are associated with the special stability of the noble gases. The
lotal numbers of electrons for these stable atoms are 2 (for He), 10 (for Ne), 18 (for
Ar), and so forth. Experimentally, it is noted that nuclei with certam numbers of pro-
tons or neutrons appear to be very stable. These numbers, called magic "LImbers and
associated with specially stable nuclei, were later explained by the shell model.
According to this theory, a magic nun:-ber is the number of nuclear particles in a
completed shell ofprotons or neutrons. Because nuclear forces differ from electri.
cal forces, these numbers are not the same as those for electrons in atoms. For pro-
tons, the magic numbers are 2, 8, 20, 28, 50, and 82. Neutrons have these same
magic numbers, as well as the magic number 126. For protons, calculations show
that 114 should also be a magic number.
Some of the evidence for these magic numbers, and therefore for the shell
model of the nucleus, is as follows. Many radioactive nuclei decay by emitting
alpha particles, or ~He nuclei. There appears to be special stability in the ~He
nucleus. It contains two protons and two neutrons; that is, it contains a magic num-
ber of protons (2) and a magic number of neutrons (also 2).
Another piece of evidence is seen in the final products obtained in natural
radioactive decay. For example, uranium-238 decays to thorium-234, which in turn
decays to protactinium-234, and so forth. Each product is radioactive and decays to
another nucleus until the final product, 2~~Pb. is reached. This nucleus is stable.
Note that it contains 82 protons, a magic number. Other radioactive decay series end
at 2~iPb and 2~~Pb, eacb of which has a magic number of protons. Note that 2~~Pb
also has a magic number of neutrons (208 - 82 = 126).
Evidence also points to the special stability of pairs of protons and pairs of neu-
trons, analogous to the stability of pairs of electrons in molecules. Table 20.1 lists
the number of stable isotopes that have an even number of protons and an even
number of neutrons (157). By comparison, only 5 stable isotopes have an odd num-
berof protons and an odd number of neutrons.
Finally, when you plot each stable nuclide on a graph with the number of pro-
tons (Z) on the horizontal axis and the number of neutrons (N) on the vertical aXIS,
these stable nuclides fall in a certain regIOn, or band, of the graph. The band of sta-
bility IS the region in which stable nuclides lie in a plot ofnLlmber ofprotons against
"umber afneutrans. Figure 20.3 shows the band of stability; the rest of the figure is
explained later in this section. For nuclides up to Z = 20, the ratio of neutrons to
protons is about 1.0 to 1.1. As Z increases, however, the neutron-to-proton ratio
increases to about 1.5. This increase in neutron-to-proton ratio with increasing Z is
believed to resuli from the increasing repulsions of protons from their electric
e)
20.1 RADIOACTIVITY 841
130
AI;t~:
e~iSSion i:i'
120
I,
..I
./
FIGURE 20,3
Band of stability. The stable
110 nuclides, indicated by black
I JJ ;1 dots, cluster in a band. Nuclides
I ~ .:/
100 to the left of the band of slabilily
Beta emission
90 /::: / usually decay by beta emission,
~ '. I whereas those to the right usu-
"c0 80 .(i,{'f'j ally decay by positron emission
b Band of 4:~:.~/ or electron capture. Nuclides of
~ 70
v
c stability----!:ilY Z> 83 often decay by alpha
~
60 emission.
0
~
~
fJty Electron capture
and
E 50 (;W,/ ->'"
= 40 positron emissiori
Z
30
A.",)i~,~.
...
13'.>fI1.'.'
... < .~
. . :.17
:/.;r-,r
20
10
0 10 m M a ~ W M W ~ 1m
Number of protons (Z)
charges. More neutrons are required to give attractive nuclear forces to offset Ihese
rt:pulsions.
It appears Ihat when the number of protons becomes very large, the
proton-prolan repulsions become so great that stable nuclides are impossible, No
stable nuclides are known with atomic numbers greater than 83, On the other hand,
all elements with Z equal to 83 or less have one or more stable nuclides, with the
exception of technetium (Z = 43), as noted in the chapter opening, and promethium
(Z = 61),
EXAMPLE 20.3
Predicting the Relative Stabilities of Nuclides
One of the nuclides in each of the following pairs is radioactive; the other is stable.
Which is radi,oactive and which is stable? Explain.
(a) 2~:PO. 2~Bi (b) ~~K, igK (c) ~:Ga, ~~Ga
PROBLEM STRATEGY
You must decide which nuclide of each patr is more likely to be stable, based on the
general principles stated in preceding text.
SOLUT10N
(a) Polonium has an atomic number greater than 83. so ~~~Po is radioactive. Bismuth-
209 has 126 neutrons (a magic number), so 2Z~Bi is expected to be stable. (b) Of these
two isotopes, iK has a magic number of neutrons (20), so i~K is expected to be sta-
ble. The isotope l~K has an odd number of protons (19) and an odd number of neu-
trons (21). Because stable odd-odd nuclei are rare, you might expect t~K to be
radioactive. (c) Of the two isotopes, j~Ga lies farther from the center of the band of
stability, so it is more likely to be radioactive. For this reason, you expect ~~Ga to be
radioactive and ilGa to be stable.
Exercise 20.3
Of the following nuclides, two are radioactive. Which are radioactive and which is sta-
ble? Explain. (a) 1;~SIl; (b) i~As; (e) 2~;Ae.
t~Ar
RADIOACTIVITY
0.012%. <] Potassium-40 can decay by electron capture, as well as by beta and
843
The product nucleus has an atomic number that is one less than that of the origi-
nal nucleus. The mass number remains the same. When another orbital electron
fills the vacancy in the inner-shell orbital created by electron caplUre, an x-ray
photon is emitted.
5. Gamma emission (abbreviated ')'): emissionfrom an excited nucleus ofa gamma
photon, corresponding to radiation with a wavelength oj about 10- 12 m: In
many cases, radioactive decay results in a product nucleus that is in an excited
state. As in the case of atoms, the excited state is unstable and goes to a lower-
energy state with the emission of electromagnetic radiation. For nuclei, this radi-
ation is in the gamma-ray region of the spectrum.
Often gamma emission occurs very quickly after radioactive decay. In some
cases, however, an excited state has significant lifetime before it emits a gamma
photon. A metastable nucleus is a nucleus in an excited state with a lifetime of
at least one nanosecond (10- 9 s). In time, the metastable nucleus decays by
gamma emission. An example is metastable technetium-99, denoted ~~mTc,
which is used in medical diagnosis, as discussed in Section 20.5.
~~m Tc ~jTc + gY
Nuclear Change
Equivalent Usual Nuclear
Type of Decay Radiation Process Atomic Number Mass Number Condition
ally seen in lighter elements (recall that phosphorus-3D decays by positron emis-
sion). However, in the very heavy elements, especially those with Z greater than 83,
radioactive decay is often by alpha emission (noted in Figure 20.3 at the top of the
figure). 2~~U, 2~gRa. and 2~5Th are examples of alpha emitters.
E~Mf'Lf~j}.4
Predicting th~ typeQ! ~dioactiveDecay
Pr~,~iGtth~':e~ped~~.tyPe of 'radioactive decay 'for each ofthe. fc"Ubw{n'g: radioaCtive
nuclides: fa) ~6C,i:',:(b) :gAl.
PROIlLEM ST\<ATEGY
Compare each nuclide with.the stable nuclides of the same element. A nuclide with an
NIZratio greatenhan that of the stable nuclides is expected to exhibit beta emiss'ion.
A nuclide with anN/I, ratio less than that of the stable nuclides is expected to exhibit
positron emission or electron capture; electron capture is important with heavier ele-
ments. Since you are comparing nuclides of the same Z, you can compare mass num~
bers (~ N + Z), rather than NIZ
SOLUTION
(a) The atomic weight of calcium is 40.1 amu, so you expect calciurn-40 to be a stable
isotope. CalciumA7 has a mass number greater than that of the stable isotope, so yoU
expect it to decay by beta emission. (ThIs is the observed behavior of calcium-47 .)
(b) The atomic weight of aluminum is 27.0 amu, so you expect aluminum-27 lO be a
stable isotope. The mass number of aluminum-25 is less than 27, so you expect alu
The nuclear reactions discussed in the previous section are radioactive decay reac-
tions, in which a nucleus spontaneously decays to another nucleus and emits a par-
ticle, such as an alpha or beta particle. In 1919, Ernest Rutherford discovered that it
is possible to change the nucleus of one element into the nucleus of another element
by processes that can be controlled in the laboratory. Transmutation is the change
of one elemelll to another by bombarding the nucleus of the element with nuclear
particles or nuclei.
Transmutation
Rutherford used a radioactive element as a source of alpha particles and allowed
these particles to collide with nitrogen nuclei. He discovered that protons are
ejected in the process. The equation for the nuclear reaction is
IjN + ~He __ I~O + lH
The experiments were repeated on other light nuclei, most of which were trans-
muted to other elements with the ejection of a proton. These experiments yielded
two significant results. First, they strengthened the view that all nuclei contain pro-
tons. Second, they showed for the first time that it is possible to change one element
into another under laboratory control.
When beryllium is bombarded with alpha particles, a penetrating radiation is
given off that is not deflected by electric or magnetic fields. Therefore, the radiation
does not consist of charged particles. The British physicist James Chadwick
(1891-1974) suggested in 1932 that the radiation from beryllium consists of neutral
particles, each with a ,mass approximately that of a proton. The particles are called
neutrons. The reaction that resulted in the discovery of the neutron is
:Be + iHe ------'lo l~C + ~n
In 1933, a nuclear bombardment reaction was used to produce the first artificial
radioactive isotope. Irene and Fn,deric Joliot-Curie found that aluminum bom-
barded with alpha particles produces phosphorus-3D, which decays by emitting
positrons. The reactions are
"AI
13 + 24He - 3 0,
ISP + on
~~P - ~~Si + ?e
Phosphorus-3D was the first radioactive nucleus produced in the laboratory. Since
then over a thousand radioactive isotopes have been made. <l
Nuclear bombardment reactions are often referred to by an. abbreviated nota-
tion. For example, the reaction
IjN + iHe ~ I~O + :H
is abbreviated '~N(a, p)';O. In this notation, you first write the nuclide symbol for
the original nucleus (target), then in parentheses you write the symbol for the pro-
jectile particle (incoming particle), followed by a comma and the symbol for the
ejected particle. After the last parenthesis. you write the nuclide symbol for the
product nucleus. The following symbols are used for particles:
Neutron n
Proton p
Deuteron, ~H d
Alpha, iHe 0:
, ,
from natural sources, rather than giving a transmutation reaction. These elements
have nuclei of large positive charge, and the alpha particle must be traveling very
fast in order to penetrate the nucleus and react. Alpha particles from natural sources
do not have sufficient kinetic energy. To shoot charged particles into heavy nuclei,
it is necessary to accelerate the charged particles.