Nuclear chemistry

Nuclear chemistry deals with the nuclei of atoms breaking apart. Atoms are continually
undergoing decay. When studying nuclear chemistry, there is a typical format used to represent
specific isotopes.

Nuclear equations are typically written in the format shown below. There are 5 different types of
radioactive decay.

1. Alpha decay follows the form:

Where A is the parent isotope (the atom being broken apart) B is the daughter isotope or the
isotope formed. When an element is broken down in alpha decay it loses two neutrons and two
(2) protons. This means that the name of the element will change as well, moving back two (2)
places on the periodic table. Alpha decay is not very penetrating because the He atoms capture
electrons before traveling very far. However it is very damaging because the alpha particles can
knock atoms off of molecules. Alpha decay is the most common in elements with an atomic
number greater than 83.

2. Beta negative decay follows the form:

The beta emission increases the atomic number by one (1) by adding one (1) proton. At the same
time, one (1) neutron is lost so the mass of the daughter isotope is the same as the parent isotope.
Beta negative decay is more penetrating than alpha decay because the particles are smaller, but
less penetrating than gamma decay. Beta electrons can penetrate through about one (1) cm of
flesh before they are brought to a halt because of electrostatic forces. Beta decay is most
common in elements with a high neutron to proton ratio.

3. Gamma decay follows the form:

In gamma emission, neither the atomic number or the mass number is changed. A high energy
gamma ray is given off when the parent isotope falls into a lower energy state. Gamma radiation
is the most penetrating of all. These photons can pass through the body and cause damage by
ionizing all the molecules in their way.

4. Positron emission (also called Beta positive decay) follows the form:

In this reaction a positron is emitted. A positron is exactly like an electron in mass and charge
force except with a positive charge. It is formed when a proton breaks into a neutron with mass
and neutral charge and this positron with no mass and the positive charge. Positron emission is
most common in lighter elements with a low neutron to proton ratio.

5. Electron capture follows the form:

Electron capture is also called K-capture since the captured electron usually comes from the
atom's K-shell.
This reaction a nucleus captures one (1) of its own atom's inner shell electrons which reduces the
atomic number by one. This captured electron joins with a proton in the nucleus to form a
neutron. Electron capture is common in larger elements with a low neutron to proton ratio.
All elements with an atomic number over 83 are considered radioactive. Radioactivity can be
measured using a Geiger counter, a cylinder containing a low-pressure gas and two
(2) electrodes. Radiation ionizes the atoms in the cylinder and allows current to flow between the
electrodes.

All radioactive elements disintegrate according to their specific half-life. The half-life of a
radioactive substance is the time required for half of the initial number of nuclei to disintegrate.
The decay rate expresses the speed at which a substance disintegrates. The following equation
represents the relationship between the number of nuclei remaining, N, the number of nuclei
initially present, N0, the rate of decay, k, and the amount of time, t.

The relationship between the half-life of a radioactive substance and k, the rate at which it
decays can also be found.

By using these equations, it is possible to calculate how much of a nuclear substance will be left
after a certain time and how much of a substance originally existed. A common example is
isotopic dating in which the ages of archeological artifacts are determined by measuring the
activity of the isotopes.

Examples
Alpha Decay Examples
The first example is the unstable seaborgium. The seaborgium atom u nderwent a
radioactive decay and in the process converted to the rutherfordium by emitting an alpha particle
as seen in the equation below:
263
Sg106 --> 259Rf104 + αα
We compare the difference in the atomic number and mass number of the seaborgium
(Sg) and rutherfordium (Rf) is two and four respectively. The difference is due to the fact that
the radioactive decay emits an alpha particle which has atomic mass and mass number of 2 and 4
respectively. So in the process the total number of sub atomic particles is conserved.

The second example is the unstable astatine. The astatine atom underwent a
radioactive decay and in the process converted to the bismuth by emitting an alpha particle as
seen in the equation below.
211
At83 --> 207Bi81 + αα
The bismuth and astatine are two places apart in the periodic table with the difference of 4 and 2
in their respective mass number and atomic mass.

The Alpha Particle Decay of Radon 198

Below is the isotope radon-198 will alpha decay to polonium-194. Alpha decay equation for
radon-198 is:
198
Rn86 ----> 194Po84 + 4He2
The radon has been shown on the left and the alpha particle, which is a helium nucleus is shown
of the right with the polonium.

Alpha Particle Decay of Uranium 238

Alpha particles played an vital role in nuclear physics before the discovery of charged
particle accelerators and were widely used in research.
The procedure of alpha decay is a nuclear reaction that can be written as:
A
Z(Z)N --------> A-4Z-2(X)2-N-2 + 42He2+ + QαQα
Where we have chosen to write out all of the superscripts and subscripts. Thus the alpha (αα)-
decay of 238U can be written as:
238
U --------> 234Th2- + 4He2+ + Q.
The Q-value is positive (exothermic) for impulsive alpha decay. The helium nucleus appears
with a substantial velocity and is entirely ionized and the atomic electrons on the daughter are
upset by the sudden change but the whole process preserves electrical charge.

Beta Decay Example

An atom of 138I53 undergoes β- decay and produces a β particle.
Write a chemical equation showing this reaction.
Solution:
Nuclear reactions need to have the sum of protons and neutrons the same on both sides of the
equation. The number of protons must also be consistent on both sides of the reaction.
β- decay occurs when a neutron converts into a proton and ejects an energetic electron called the
beta particle. This means the number of neutrons, N, is reduced by 1 and the number of protons,
A, is increased by 1 on the daughter atom.
138
I53 → ZXA + 0e-1
A = number of protons = 53 + 1 = 54
X = the element with atomic number = 54
According to the periodic table, X = xenon or Xe
The mass number, A, remains unchanged because the loss of one neutron is offset by the gain of
a proton.
Z = 138
Substitute these values into the reaction:
I53 → 138Xe54 + 0e-1
138

Gamma Decay Example

Some examples of gamma emission are as follows.
56Ba
137
→→ 56Ba137 + γγ rays

5B
12
→→ beta particle + Anti neutrino+ 6C12 →→ 6C12 + γγ rays
66Dy
152
→→ 66Dy152 + γγ rays

77Ir
192
→→ 78Pt192 + -1e0+ γγ rays

Positron Decay Example

Two points to remember about positron decay:
1. It emits a positron and a neutrino.
2. The atomic number decreases by one, and the mass number is unchanged.
Here is an example of a positron decay equation:
2312Mg→2311Na+01e+00ν
Practice problems:
Complete the following positron decay equations.
(a) 7535Br→?+01e+00ν
(b) ?→3014Si+01e+00ν
(c) 2714Si→?+00ν
(d) ?→4521Sc+?
(e) 85B→?
Solutions
(a) 7535Br→7534Se+01e+00ν
(b) 3015P→3014Si+01e+00ν
(c) 2714Si→2713Al+01e+00ν
(d) 4522Ti→4521Sc+01e+00ν
(e) 85B→84Be+01e+00ν

Electron Capture Example

An atom of 13N7 undergoes electron capture and produces a gamma radiation photon.
Write a chemical equation showing this reaction.
Solution:
Nuclear reactions need to have the sum of protons and neutrons the same on both sides of the
equation. The number of protons must also be consistent on both sides of the reaction.
Electron capture decay occurs when a K- or L-shell electron is absorbed into the nucleus and
converts a proton into a neutron. This means the number of neutrons, N, is increased by 1 and the
number of protons, A, is decreased by 1 on the daughter atom. The energy level change of the
electron produces a gamma photon.
13
Na7 + + 0e-1 → ZXA + γ
A = number of protons = 7 - 1 = 6
X = the element with atomic number = 6
According to the periodic table, X = Carbon or C.
The mass number, A, remains unchanged because the loss of one proton is offset by the addition
of a neutron.
Z = 13
Substitute these values into the reaction:
13
N7 + e- → 13C6 + γ
 Atomic Models and the Quantum Numbers
There are different models of the structure of the atom. One of the first models was created by
Niels Bohr, a Danish physicist. He proposed a model in which electrons circle the nucleus in
"orbits" around the nucleus, much in the same way as planets orbit the sun. Each orbit represents
an energy level which can be determined using equations generated by Planck and others
discussed in more detail below. The Bohr model was later proven to be incorrect, but provides a
useful model for building an explanation.

The "accepted" model is the quantum model. In the quantum model, we state that the electron
cannot be found precisely, but we can predict the probability, or likelihood, of an electron being
at some location in the atom. You should be familiar with quantum numbers, a series of three
numbers used to describe the location of some object (like an electron) in three-dimensional
space:
1. n: the principal quantum number, an integer value (1, 2, 3...) that is used to describe
the quantum level, or shell, in which an electron resides. The principal quantum
number is the primary number used to determine the amount of energy in an atom.
Using one of the first important equations in atomic structure (developed by Niels
Bohr), we can calculate the amount of energy in an atom with an electron at some
value of n:
Rhc
En = -
n2
where:
R = Rydberg constant, a value of 1.097 X 107 m-1
c = speed of light, 3.00 X 108 m/s
h = Planck's constant, 6.63 X 10 -34 J-s
n = principal quantum number, no unit
For example, how much energy does one electron with a principal quantum number of n= 2
have?
Rhc
En = -
n2
or
(1.097x107 m-1 ∗ (6.63x10-34 J•s)∗(3.0x108 m•s-1)
En = -
22
= 5.5x10-19 J
You might ask, well, who cares? In addition to the importance of knowing how much energy is
in an atom (a very important characteristic!), we can also derive, or calculate, other information
from this energy value. For example, can we see this energy? The table below suggests that we
can. For example, suppose that an electron starts at the n=3 level (we'll call this the excited state)
and it falls down to n=1 (the ground state). We can calculate the change in energy using the
equation:
1 1
ΔE = hv = RH -
ni2 nf2
Where:
ΔE = change in energy (Joules)
h = Planck's constant with a value of 6.63 x 10-34 (J-s)
ν is frequency (s-1)
RH is the Rydberg constant with a value of 2.18 x 10-18J.
ni is the initial quantum number
nf is the final quantum number
Using the equation below, we can calculate the wavelength and the frequency of the energy. The
wavelength and the frequency give us information about how we might "see" the energy:
vλ = c
Where:
ν = the frequency of radiation (s-1)
λ = the wavelength (m)
c = the speed of light with a value of 3.00 x 108 m/s in a vacuum

Speed of light = 3.00E+08

Rydberg constant = 2.18E-18
Planck's constant = 6.63E-34

Excited state, n = 3 4 5
Ground state, n = 2 2 2
Excited state energy (J) 2.42222E-19 1.363E-19 8.72E-20
Ground state energy (J) 5.45E-19 5.45E-19 5.45E-19
ΔE = -3.02778E-19 -4.09E-19 -4.58E-19
ν= 4.56678E+14 6.165E+14 6.905E+14
λ(nm) = 656.92 486.61 434.47

2. l ("el", not the number 1): the azimuthal quantum number, a number that specifies a
sublevel, or subshell, in an orbital. The value of the azimuthal quantum number is
always one less than the principal quantum number n. For example, if n=1, then
"el"=0. If n=3, then l can have three values: 0,1, and 2. The values of l are typically
not identified as "0, 1, 2, and 3" but are more commonly called by their historic
names, "s, p, d, and f", respectively. Since the quantum numbers were discovered
through the study of light and lines on an electromagnetic spectra, chemists identified
the lines by their quality: sharp, principal, diffuse and fundamental. The table below
shows the relationship:
Value of l Subshell designation
0 s
1 p
2 d
3 f
3. m: the magnetic quantum number. Each subshell is composed of one or more orbitals.
In the study of light, it was discovered that additional lines appeared in the spectra
produced when light was emitted in a magnetic field. The magnetic quantum number
has values between -l and +l. When l =1, for example, m can have three values: -1, 0,
and +1. Because you know from the chart above that the subshell designation for l =1
is "p", you now know that the p orbital has three components. In your study of
chemistry, you will be presented with px, py, and pz. Notice how the subscripts are
related to a three-dimensional coordinate system, x, y, and z. The chart below shows a
summary of the quantum numbers:
Principal Azimuthal Magnetic Number of
Subshell
Quantum Quantum Quantum orbitals in
Designation
Number (n) Number (l) Number (m) subshell
1 0 1s 0 1
2 0 2s 0 1
 1 2p -1 0 +1 3
0 3s 0 1
3 1 3p -1 0 +1 3
2 3d -2 -1 0 +1 +2 5
0
0 4s 1
-1 0 +1
1 4p 3
4 -2 -1 0 +1 +2
2 4d 5
-3 -2 -1 0 +1
3 4f 7
+2 +3

Chemists care about where electrons are in an atom or a molecule.

In the early models, we believed that electrons move like billiard
balls, and followed the rules of classical physics. The graphic below
attempts to show that earlier models thought that we could identify
the exact path, position, velocity, etc. of an electron or electrons in
an atom:

A more accurate picture is that the electron(s) reside in a "cloud" that

surrounds the nucleus of the atom. This concept is shown in the
graphic below:

Chemists are interested in predicting the probability that the

electron will be at some particular part of this cloud. The cloud is
better known as an orbital, and comes in several different types, or
shapes. Atomic orbitals are known as s, p, d, and f orbitals. Each
type of atomic orbital has certain characteristics, such as shape. For
example, as the graphic below shows, an s orbital is spherical in
shape:

On this graph, the horizontal (x) axis represents the distance from the nucleus in units of a0, or
atomic units. The value of a0 is 0.0529 nanometers (nm). The vertical (y) axis represents the
probability density. What you should notice is that as the electron moves farther away from the
nucleus, the probability of its being found at that distance decreases. In other words, the electron
prefers to hang around close to the nucleus.
The three graphics below show some other orbitals. The first graph (top left) is of a "2s" orbital.
Each "s" orbital can hold two electrons in its cloud. Notice how there is a relatively high
probability of an electron being near the nucleus, then some space where the probability is close
to zero, then the probability increases substantially at some distance from the nucleus. The
graphic at the top right shows a "2p" atomic orbital. Orbitals that are "p" orbitals can hold up to
six (6) electrons in their cloud. Notice its "dumbbell" or "figure of eight" shape. At the bottom
left is a "3s" orbital. Again, notice its spherical shape. Finally, at the bottom right, is a "3p"
orbital.