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The energy needed to remove one or more electrons from a neutral atom to form a positively
charged ion is a physical property that influences the chemical behavior of the atom. By
definition, the first ionization energy of an element is the energy needed to remove the
outermost, or highest energy, electron from a neutral atom in the gas phase.
The process by which the first ionization energy of hydrogen is measured would be
represented by the following equation.
Practice Problem 3:
Use the Bohr model to calculate the wavelength and energy of the photon that would have to
be absorbed to ionize a neutral hydrogen atom in the gas phase.
The magnitude of the first ionization energy of hydrogen can be brought into perspective by
comparing it with the energy given off in a chemical reaction. When we burn natural gas,
about 800 kJ of energy is released per mole of methane consumed.
The thermite reaction, which is used to weld iron rails, gives off about 850 kJ of energy per
mole of iron oxide consumed.
The first ionization energy for helium is slightly less than twice the ionization energy for
hydrogen because each electron in helium feels the attractive force of two protons, instead of
one.
It takes far less energy, however, to remove an electron from a lithium atom, which has three
protons in its nucleus.
This can be explained by noting that the outermost, or highest energy, electron on a lithium
atom is in the 2s orbital. Because the electron in a 2s orbital is already at a higher energy than
the electrons in a 1s orbital, it takes less energy to remove this electron from the atom.
The first ionization energies for the main group elements are given in the two figures below.
In general, the first ionization energy increases as we go from left to right across a
row of the periodic table.
The first ionization energy decreases as we go down a column of the periodic table.
The first trend isn't surprising. We might expect the first ionization energy to become larger
as we go across a row of the periodic table because the force of attraction between the
nucleus and an electron becomes larger as the number of protons in the nucleus of the atom
becomes larger.
The second trend results from the fact that the principal quantum number of the orbital
holding the outermost electron becomes larger as we go down a column of the periodic table.
Although the number of protons in the nucleus also becomes larger, the electrons in smaller
shells and subshells tend to screen the outermost electron from some of the force of attraction
of the nucleus. Furthermore, the electron being removed when the first ionization energy is
measured spends less of its time near the nucleus of the atom, and it therefore takes less
energy to remove this electron from the atom.
The figure below shows the first ionization energies for elements in the second row of the
periodic table. Although there is a general trend toward an increase in the first ionization
energy as we go from left to right across this row, there are two minor inversions in this
pattern. The first ionization energy of boron is smaller than beryllium, and the first ionization
energy of oxygen is smaller than nitrogen.
But there is an important difference in the way electrons are distributed in these atoms.
Hund's rules predict that the three electrons in the 2p orbitals of a nitrogen atom all have the
same spin, but electrons are paired in one of the 2p orbitals on an oxygen atom.
Hund's rules can be understood by assuming that electrons try to stay as far apart as possible
to minimize the force of repulsion between these particles. The three electrons in the 2p
orbitals on nitrogen therefore enter different orbitals with their spins aligned in the same
direction. In oxygen, two electrons must occupy one of the 2p orbitals. The force of repulsion
between these electrons is minimized to some extent by pairing the electrons. There is still
some residual repulsion between these electrons, however, which makes it slightly easier to
remove an electron from a neutral oxygen atom than we would expect from the number of
protons in the nucleus of the atom.
Practice Problem 4:
Predict which element in each of the following pairs has the larger first ionization energy.
(a) Na or Mg
(b) Mg or Al
(b) Mg or Al
(c) F or Cl
The first ionization energy of sodium, for example, is the energy it takes to remove one
electron from a neutral atom.
The second ionization energy is the energy it takes to remove another electron to form an
Na2+ ion in the gas phase.
The energy required to form a Na3+ ion in the gas phase is the sum of the first, second, and
third ionization energies of the element.
It doesn't take much energy to remove one electron from a sodium atom to form an Na+ ion
with a filled-shell electron configuration. Once this is done, however, it takes almost 10 times
as much energy to break into this filled-shell configuration to remove a second electron.
Because it takes more energy to remove the second electron than is given off in any chemical
reaction, sodium can react with other elements to form compounds that contain Na+ ions but
not Na2+ or Na3+ ions.
A similar pattern is observed when the ionization energies of magnesium are analyzed. The
first ionization energy of magnesium is larger than sodium because magnesium has one more
proton in its nucleus to hold on to the electrons in the 3s orbital.
The second ionization energy of Mg is larger than the first because it always takes more
energy to remove an electron from a positively charged ion than from a neutral atom. The
third ionization energy of magnesium is enormous, however, because the Mg2+ ion has a
filled-shell electron configuration.
The same pattern can be seen in the ionization energies of aluminum. The first ionization
energy of aluminum is smaller than magnesium. The second ionization energy of aluminum
is larger than the first, and the third ionization energy is even larger. Although it takes a
considerable amount of energy to remove three electrons from an aluminum atom to form an
Al3+ ion, the energy needed to break into the filled-shell configuration of the Al3+ ion is
astronomical. Thus, it would be a mistake to look for an Al4+ ion as the product of a chemical
reaction.
Practice Problem 5:
Predict the group in the periodic table in which an element with the following ionization
energies would most likely be found.
2nd IE = 1577
3rd IE = 3232
4th IE = 4355
5th IE = 16,091
6th IE = 19,784
Practice Problem 6:
Use the trends in the ionization energies of the elements to explain the following
observations.
(a) Elements on the left side of the periodic table are more likely than those on the right to
form positive ions.
(b) The maximum positive charge on an ion is equal to the group number of the element
Ionization energies measure the tendency of a neutral atom to resist the loss of electrons. It
takes a considerable amount of energy, for example, to remove an electron from a neutral
fluorine atom to form a positively charged ion.
The electron affinity of an element is the energy given off when a neutral atom in the gas
phase gains an extra electron to form a negatively charged ion. A fluorine atom in the gas
phase, for example, gives off energy when it gains an electron to form a fluoride ion.
Electron affinities are more difficult to measure than ionization energies and are usually
known to fewer significant figures. The electron affinities of the main group elements are
shown in the figure below.
At first glance, there appears to be no pattern in electron affinity across a row of the periodic
table, as shown in the figure below.
When these data are listed along with the electron configurations of these elements, however,
they make sense. These data can be explained by noting that electron affinities are much
smaller than ionization energies. As a result, elements such as helium, beryllium, nitrogen,
and neon, which have unusually stable electron configurations, have such small affinities for
extra electrons that no energy is given off when a neutral atom of these elements picks up an
electron. These configurations are so stable that it actually takes energy to force one of these
elements to pick up an extra electron to form a negative ion.
Electron Affinities and Electron Configurations for the First 10 Elements in the Periodic
Table
Students often believe that sodium reacts with chlorine to form Na+ and Cl- ions because
chlorine atoms "like" electrons more than sodium atoms do. There is no doubt that sodium
reacts vigorously with chlorine to form NaCl.
Furthermore, the ease with which solutions of NaCl in water conduct electricity is evidence
for the fact that the product of this reaction is a salt, which contains Na+ and Cl- ions.
H2O Na+(aq)
NaCl(s) -
+ Cl (aq)
The only question is whether it is legitimate to assume that this reaction occurs because
chlorine atoms "like" electrons more than sodium atoms.
The first ionization energy for sodium is one and one-half times larger than the electron
affinity for chlorine.