Nuclear chemistry is the study of reactions that involve changes in nuclear structure. The chapter on atoms, molecules, and ions introduced the basic idea of nuclear structure, that the nucleus of an atom is composed of protons and, with the exception of [latex]{}_{1}^{1}\text{H}[/latex], neutrons. Recall that the number of protons in the nucleus is called the atomic number (Z) of the element, and the sum of the number of protons and the number of neutrons is the mass number (A). Atoms with the same atomic number but different mass numbers are isotopes of the same element. When referring to a single type of nucleus, we often use the term nuclide and identify it by the notation [latex]{}_{\text{Z}}^{\text{A}}\text{X}[/latex], where X is the symbol for the element, A is the mass number, and Z is the atomic number (for example, [latex]{}_{16}^{14}\text{C}[/latex] ). Often a nuclide is referenced by the name of the element followed by a hyphen and the mass number. For example, [latex]{}_{16}^{14}\text{C}[/latex] is called “carbon-14.”

Protons and neutrons, collectively called nucleons, are packed together tightly in a nucleus. With a radius of about 10⁻¹⁵ meters, a nucleus is quite small compared to the radius of the entire atom, which is about 10⁻¹⁰ meters. Nuclei are extremely dense compared to bulk matter, averaging 1.8 [latex]\times[/latex] 10¹⁴ grams per cubic centimeter. For example, water has a density of 1 gram per cubic centimeter, and iridium, one of the densest elements known, has a density of 22.6 g/cm³. If the earth’s density were equal to the average nuclear density, the earth’s radius would be only about 200 meters (earth’s actual radius is approximately 6.4 [latex]\times[/latex] 10⁶ meters, 30,000 times larger). Example 1 demonstrates just how great nuclear densities can be in the natural world.

To hold positively charged protons together in the very small volume of a nucleus requires very strong attractive forces because the positively charged protons repel one another strongly at such short distances. The force of attraction that holds the nucleus together is the strong nuclear force. (The strong force is one of the four fundamental forces that are known to exist. The others are the electromagnetic force, the gravitational force, and the nuclear weak force.) This force acts between protons, between neutrons, and between protons and neutrons. It is very different from the electrostatic force that holds negatively charged electrons around a positively charged nucleus (the attraction between opposite charges). Over distances less than 10⁻¹⁵ meters and within the nucleus, the strong nuclear force is much stronger than electrostatic repulsions between protons; over larger distances and outside the nucleus, it is essentially nonexistent.

Nuclear Binding Energy

As a simple example of the energy associated with the strong nuclear force, consider the helium atom composed of two protons, two neutrons, and two electrons. The total mass of these six subatomic particles may be calculated as:

[latex]\begin{array}{ccccccc}\left(2\times \text{1.0073 amu}\right)&+& \left(2\times \text{1.0087 amu}\right)&+& \left(2\times \text{0.00055 amu}\right)&=& \text{4.0331 amu}\\ \text{protons}&& \text{neutrons}& &\text{electrons}\end{array}[/latex]

However, mass spectrometric measurements reveal that the mass of an [latex]{}_{2}{}^{4}\text{He}[/latex] atom is 4.0026 amu, less than the combined masses of its six constituent subatomic particles. This difference between the calculated and experimentally measured masses is known as the mass defect of the atom. In the case of helium, the mass defect indicates a “loss” in mass of 4.0331 amu – 4.0026 amu = 0.0305 amu. The loss in mass accompanying the formation of an atom from protons, neutrons, and electrons is due to the conversion of that mass into energy that is evolved as the atom forms. The nuclear binding energy is the energy produced when the atoms’ nucleons are bound together; this is also the energy needed to break a nucleus into its constituent protons and neutrons. In comparison to chemical bond energies, nuclear binding energies are vastly greater, as we will learn in this section. Consequently, the energy changes associated with nuclear reactions are vastly greater than are those for chemical reactions.

The conversion between mass and energy is most identifiably represented by the mass-energy equivalence equation as stated by Albert Einstein:

[latex]E=m{c}^{2}[/latex]

where E is energy, m is mass of the matter being converted, and c is the speed of light in a vacuum. This equation can be used to find the amount of energy that results when matter is converted into energy. Using this mass-energy equivalence equation, the nuclear binding energy of a nucleus may be calculated from its mass defect, as demonstrated in Example 2. A variety of units are commonly used for nuclear binding energies, including electron volts (eV), with 1 eV equaling the amount of energy necessary to the move the charge of an electron across an electric potential difference of 1 volt, making 1 eV = 1.602 [latex]\times[/latex] 10^–19 J.

Because the energy changes for breaking and forming bonds are so small compared to the energy changes for breaking or forming nuclei, the changes in mass during all ordinary chemical reactions are virtually undetectable. As described in the chapter on thermochemistry, the most energetic chemical reactions exhibit enthalpies on the order of thousands of kJ/mol, which is equivalent to mass differences in the nanogram range (10^–9 g). On the other hand, nuclear binding energies are typically on the order of billions of kJ/mol, corresponding to mass differences in the milligram range (10^–3 g).

Nuclear Stability

A nucleus is stable if it cannot be transformed into another configuration without adding energy from the outside. Of the thousands of nuclides that exist, about 250 are stable. A plot of the number of neutrons versus the number of protons for stable nuclei reveals that the stable isotopes fall into a narrow band. This region is known as the band of stability (also called the belt, zone, or valley of stability). The straight line in Figure 1 represents nuclei that have a 1:1 ratio of protons to neutrons (n:p ratio). Note that the lighter stable nuclei, in general, have equal numbers of protons and neutrons. For example, nitrogen-14 has seven protons and seven neutrons. Heavier stable nuclei, however, have increasingly more neutrons than protons. For example: iron-56 has 30 neutrons and 26 protons, an n:p ratio of 1.15, whereas the stable nuclide lead-207 has 125 neutrons and 82 protons, an n:p ratio equal to 1.52. This is because larger nuclei have more proton-proton repulsions, and require larger numbers of neutrons to provide compensating strong forces to overcome these electrostatic repulsions and hold the nucleus together.

Figure 1. This plot shows the nuclides that are known to exist and those that are stable. The stable nuclides are indicated in blue, and the unstable nuclides are indicated in green. Note that all isotopes of elements with atomic numbers greater than 83 are unstable. The solid line is the line where n = Z.

The nuclei that are to the left or to the right of the band of stability are unstable and exhibit radioactivity. They change spontaneously (decay) into other nuclei that are either in, or closer to, the band of stability. These nuclear decay reactions convert one unstable isotope (or radioisotope) into another, more stable, isotope. We will discuss the nature and products of this radioactive decay in subsequent sections of this chapter.

Several observations may be made regarding the relationship between the stability of a nucleus and its structure. Nuclei with even numbers of protons, neutrons, or both are more likely to be stable (see Table 1). Nuclei with certain numbers of nucleons, known as magic numbers, are stable against nuclear decay. These numbers of protons or neutrons (2, 8, 20, 28, 50, 82, and 126) make complete shells in the nucleus. These are similar in concept to the stable electron shells observed for the noble gases. Nuclei that have magic numbers of both protons and neutrons, such as [latex]{}_{2}^{4}\text{He}[/latex], [latex]{}_{18}^{16}\text{O}[/latex], [latex]{}_{20}^{40}\text{Ca}[/latex], and [latex]{}_{182}^{208}\text{Pb}[/latex], are called “double magic” and are particularly stable. These trends in nuclear stability may be rationalized by considering a quantum mechanical model of nuclear energy states analogous to that used to describe electronic states earlier in this textbook. The details of this model are beyond the scope of this chapter.

The relative stability of a nucleus is correlated with its binding energy per nucleon, the total binding energy for the nucleus divided by the number or nucleons in the nucleus. For instance, we saw in Example 2 that the binding energy for a [latex]{}_{2}^{4}\text{He}[/latex] nucleus is 28.4 MeV. The binding energy per nucleon for a [latex]{}_{2}^{4}\text{He}[/latex] nucleus is therefore:

[latex]\frac{\text{28.4 MeV}}{\text{4 nucleons}}=\text{7.10 MeV/nucleon}[/latex]

In Example 3, we learn how to calculate the binding energy per nucleon of a nuclide on the curve shown in Figure 2.

Figure 2. The binding energy per nucleon is largest for nuclides with mass number of approximately 56.

Glossary

band of stability: (also, belt of stability, zone of stability, or valley of stability) region of graph of number of protons versus number of neutrons containing stable (nonradioactive) nuclides

binding energy per nucleon: total binding energy for the nucleus divided by the number of nucleons in the nucleus

electron volt (eV): measurement unit of nuclear binding energies, with 1 eV equaling the amount energy due to the moving an electron across an electric potential difference of 1 volt

magic number: nuclei with specific numbers of nucleons that are within the band of stability

mass defect: difference between the mass of an atom and the summed mass of its constituent subatomic particles (or the mass “lost” when nucleons are brought together to form a nucleus)

mass-energy equivalence equation: Albert Einstein’s relationship showing that mass and energy are equivalent

nuclear binding energy: energy lost when an atom’s nucleons are bound together (or the energy needed to break a nucleus into its constituent protons and neutrons)

nuclear chemistry: study of the structure of atomic nuclei and processes that change nuclear structure

nucleon: collective term for protons and neutrons in a nucleus

nuclide: nucleus of a particular isotope

radioactivity: phenomenon exhibited by an unstable nucleon that spontaneously undergoes change into a nucleon that is more stable; an unstable nucleon is said to be radioactive

radioisotope: isotope that is unstable and undergoes conversion into a different, more stable isotope

strong nuclear force: force of attraction between nucleons that holds a nucleus together