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In the SparkNote on the Periodic table we discussed a number of simple periodic trends. In this section we will discuss a number of more complex trends, the understanding of which relies on knowledge of atomic structure.
Before getting into these trends, we should engage a quick review and establish some terminology. As seen in the previous section on the octet rule, atoms tend to lose or gain electrons in order to attain a full valence shell and the stability a full valence shell imparts. Because electrons are negatively charged, an atom becomes positively or negatively charged as it loses or gains an electron, respectively. Any atom or group of atoms with a net charge (whether positive or negative) is called an ion. A positively charged ion is a cation while a negatively charged ion is an anion.
Now we are ready to discuss the periodic trends of atomic size, ionization energy, electron affinity, and electronnegativity.
Atomic Size (Atomic Radius)
The atomic size of an atom, also called the atomic radius, refers to the distance between an atom's nucleus and its valence electrons. Remember, the closer an electron is to the nucleus, the lower its energy and the more tightly it is held.
Moving Across a Period
Moving from left to right across a period, the atomic radius decreases. The nucleus of the atom gains protons moving from left to right, increasing the positive charge of the nucleus and increasing the attractive force of the nucleus upon the electrons. True, electrons are also added as the elements move from left to right across a period, but these electrons reside in the same energy shell and do not offer increased shielding.
Moving Down a Group
The atomic radius increases moving down a group. Once again protons are added moving down a group, but so are new energy shells of electrons. The new energy shells provide shielding, allowing the valence electrons to experience only a minimal amount of the protons' positive charge.
Cations and Anions
Cations and anions do not actually represent a periodic trend in terms of atomic radius, but they do affect atomic radius, and so we will discuss them here.
A cation is positively charged, meaning that it is an atom that has lost an electron or electrons. The positive charge of the nucleus is thus distributed over a smaller number of electrons and electron-electron repulsion is decreased, meaning that the electrons are held more tightly and the atomic radius is smaller than in the normal neutral atom. Anions, conversely, are negatively charged ions: atoms that have gained electrons. In anions, electron-electron repulsion increases and the positive charge of the nucleus is distributed over a large number of electrons. Anions have a greater atomic radius than the neutral atom from which they derive.
The process of gaining or losing an electron requires energy. There are two common ways to measure this energy change: ionization energy and electron affinity.
Ionization Energy
The ionization energy is the energy it takes to fully remove an electron from the atom. When several electrons are removed from an atom, the energy that it takes to remove the first electron is called the first ionization energy, the energy it takes to remove the second electron is the second ionization energy, and so on. In general, the second ionization energy is greater than first ionization energy. This is because the first electron removed feels the effect of shielding by the second electron and is therefore less strongly attracted to the nucleus. If a particular ionization energy follows a previous electron loss that emptied a subshell, the next ionization energy will take a rather large leap, rather than follow its normal gently increasing trend. This fact helps to show that just as electrons are more stable when they have a full valence shell, they are also relatively more stable when they at least have a full subshell.
Ionization Energy Across a Period
very negative electron affinities, meaning they give off a great deal of energy upon gaining an electron and become more stable. Be careful, though: the nobel gases, located in the extreme right hand column of the periodic table do not conform to this trend. Noble gases have full valence shells, are very stable, and do not want to add more electrons: noble gas electron affinities are positive. Similarly, atoms with full subshells also have more positive electron affinities (are less attractive of electrons) than the elements around them.
Electron Affinities Down a Group
Electron affinities change little moving down a group, though they do generally become slightly more positive (less attractive toward electrons). The biggest exception to this rule are the third period elements, which often have more negative electron affinities than the corresponding elements in the second period. For this reason, Chlorine, Cl, (group VIIa and period 3) has the most negative electron affinity.
Electronegativity refers to the ability of an atom to attract the electrons of another atom to it when those two atoms are associated through a bond. Electronegativity is based on an atom's ionization energy and electron affinity. For that reason, electronegativity follows similar trends as its two constituent measures.
Electronegativity generally increases moving across a period and decreases moving down a group. Flourine (F), in group VIIa and period 2, is the most powerfully electronegative of the elements. Electronegativity plays a very large role in the processes of Chemical Bonding.
