how does the electron configuration of an

element—the distribution of electrons

within the orbitals of its atoms—relate to
its chemical and physical properties?
 The most successful organizing scheme
was proposed by the Russian chemist
Dmitri Mendeleev.

In 1870, he arranged the 65 elements then

known into a periodic table of rows and
columns and summarized their behavior in
the periodic law: when arranged by atomic
mass, the elements exhibit a periodic
recurrence of similar properties.
Mendeleev and the German chemist Julius
Lothar Meyer arrived at virtually the same
organization simultaneously, yet
independently.
Mendeleev focused on chemical properties
and Meyer on physical
properties.
The greater credit has gone to Mendeleev
because he was able to predict the
properties of several as-yet-undiscovered
elements, for which he had left blank
spaces in his table.
Elements are now arranged in order of
atomic number (number of protons)
rather than atomic mass.
 “no two electrons in the
same atom can have the same four
quantum numbers”

Because the spin quantum number (𝑚𝑠 )

can have only two values, the major
consequence of the exclusion principle is
that an atomic orbital can hold a maximum
of two electrons, and they must have
opposing spins.
Wolfgang Pauli
electrostatic interaction:
attraction between nucleus and electron
electron-electron repulsions
energy-level splitting
the splitting of energy levels into sublevels of differing
energies: the energy of an orbital in a many-electron atom
depends mostly on its n value (size) and to a lesser extent on
its l value (shape)
 reasons for
this energy
difference:

nuclear electron
orbital shape
charge, repulsions,

Their interplay leads to the phenomena of shielding and

penetration, which occur in all the atoms in the periodic table—
except hydrogen.
The Effect of Nuclear Charge (Z) on Orbital Energy
• Nuclear protons create an ever-present pull on the electrons.
• higher charges attract each other more strongly than lower charges
(Coulomb’s law)
“ Higher nuclear charge lowers orbital energy (stabilizes the system) by
increasing nucleus-electron attractions.”
Compare the 1 s orbital energies of three species with one electron—the
H atom ( Z = 1), He+1 ion ( Z = 2), and Li+2 ion ( Z = 3)
Which is the least stable (highest energy) 1s orbital?
Shielding: The Effect of Electron Repulsions on Orbital Energy
• Each electron “feels” not only the attraction to the nucleus but also the
repulsion from other electrons.
• This repulsion counteracts the nuclear attraction somewhat, making each
electron easier to remove by, in effect, helping to push it away.
Shielding (also called screening) reduces the full nuclear charge to an
effective nuclear charge (𝑍𝑒𝑓𝑓 ), the nuclear charge an electron experiences.
This lower nuclear charge makes the electron easier to remove.
Shielding by inner electrons greatly lowers the 𝒁𝒆𝒇𝒇 felt by outer electrons.
For a given n value, the lower the l value, the lower
the sublevel energy:
Order of sublevel energies: s ˂ p ˂ d ˂ f
electron configurations—the distributions of electrons within an atoms’
orbitals.

The recurring pattern in electron configurations is the basis for the recurring
pattern in chemical behavior.
Start at the beginning of the periodic table and add one electron per element to
the lowest-energy orbital available. (Of course, one proton and one or more
neutrons are also added to the nucleus.)

aufbau principle (German aufbauen, “to build up”) → results in ground-state

electron configurations
assign sets of quantum numbers to the electrons in the ground state of the first 10
elements
Here are two common ways to designate the
orbital and its electrons:

1. The electron configuration. This shorthand notation consists of the principal

energy level (n value), the letter designation of the sublevel (l value), and the
number of electrons (#) in the sublevel, written as a superscript: nl # .

2. The orbital diagram. An orbital diagram consists of a box (or circle, or just a
line) for each orbital in a given energy level, grouped by sublevel, with an arrow
indicating an electron and its spin. (Traditionally, ↑ is and ↓ is , but these are
arbitrary; it is necessary only to be consistent.
the energy of the sublevels increases from left to right
Hund’s rule: when orbitals of equal energy are available, the electron
configuration of lowest energy
has the maximum number of unpaired electrons with parallel spins.
One of the central points in all chemistry is that similar outer electron
configurations correlate with similar chemical behavior.
• In Group 1A(1), lithium and sodium have the outer electron configuration ns¹ (where n is the
quantum number of the outermost energy level), as do all other alkali metals (K, Rb, Cs, Fr). All
are highly reactive metals that form ionic compounds with nonmetals with formulas such as MCl,
M₂O, and M₂S (where M represents the alkali metal) and react vigorously with water to displace
H₂.
• In Group 7A(17), fluorine and chlorine have the outer electron configuration ns² np⁵ , as do the
other halogens (Br, I, At). Little is known about rare, radioactive astatine (At), but all the others
are reactive nonmetals that occur as diatomic molecules, X₂ (where X represents the halogen).
All form ionic compounds with metals (KX, MgX₂), covalent compounds with hydrogen (HX) that
yield acidic solutions in water, and covalent compounds with carbon (CX₄).
• In Group 8A(18), helium has the electron configuration ns² , and all the others have the outer
configuration ns² np⁶ . Consistent with their filled energy levels, all of these elements are
extremely unreactive monatomic gases
To summarize the major connection between quantum mechanics and
chemical periodicity: orbitals are filled in order of increasing energy, which
leads to outer electron configurations that recur periodically, which leads
to chemical properties that recur periodically.
• The 3d orbitals are filled in Period 4.
• The 4s orbital is filled before the 3d.
This switch in filling order is due to the shielding and penetration effects.
• The 4s orbital is slightly lower in energy than the 3d, and so fills first.
Similarly, the 5s orbital fills before the 4d, and the 6s fills before the 5d. In
general, the ns sublevel fills before the (n - 1)d sublevel. As we proceed
through the transition series, however, you’ll see several exceptions to this
pattern because the energies of the ns and (n - 1)d sublevels become
extremely close at higher values of n.
The anomalous filling patterns in Cr and Cu lead us
to conclude that half-filled and filled sublevels are
unexpectedly stable.
Similar Outer Electron Configurations Within a Group
Elements in a group have similar chemical properties because they have
similar outer electron configurations. Among the main-group elements (A
groups)— the s-block and p-block elements—outer electron configurations within
a group are essentially identical, as shown by the group headings in Figure 8.5.
Some variations in the transition elements (B groups, d block) and inner transition
elements ( f block) occur.
Orbital Filling Order
When the elements are “built up” by filling their levels and sublevels in order of
increasing energy, we obtain the actual sequence of elements in the periodic
table (Figure 8.6).
Group and Period Numbers Key information is embedded in the periodic table:
1. Among the main-group elements (A groups), the group number equals the number of
outer electrons (those with the highest n): chlorine (Cl; Group 7A) has 7 outer
electrons, tellurium (Te; Group 6A) has 6, and so forth.
2. The period number is the n value of the highest energy level. Thus, in Period 2, the n
= 2 level has the highest energy; in Period 5, it is the n 5 level. 3. The n value
squared (n² ) gives the total number of orbitals in that energy level. Because an
orbital can hold no more than two electrons (exclusion principle), 2n² gives the
maximum number of electrons (or elements) in the energy level. For example, for the
n = 3 level, the number of orbitals is n² = 9: one 3s, three 3p, and five 3d. The
number of electrons is 2n² , or 18: two 3s and six 3p electrons occur in the eight
elements of Period 3, and ten 3d electrons are added in the ten transition elements
of Period 4.
transition elements, those in which f orbitals are being filled
lanthanides (or rare earths), so called because they occur after and are similar
to lanthanum.
actinides, which fill the 5f orbitals that appear in Period 7 after actinium (Ac; Z =
89).

SAMPLE PROBLEM Determining Electron Configurations Problem

Using the periodic table, give the full and condensed electron configurations for
the following elements: (a) Potassium (K; Z = 19) (b) Molybdenum (Mo; Z = 42)
(c) Lead (Pb; Z = 82)
 All physical and chemical behavior of the elements is
based ultimately on the electron configuration.

• atomic size,
• ionization energy (the energy required These properties are periodic: they
to remove an electron from a gaseous generally increase and decrease in a
atom), recurring manner throughout the periodic
• electron affinity (the energy change table.
involved in adding an electron to a
gaseous atom).
Trends Among the Main-Group Elements
1. Changes in n. As the principal quantum number (n) increases, the
probability that the outer electrons will spend more time farther from the
nucleus increases as well; thus, the atoms are larger.
2. Changes in 𝑍𝑒𝑓𝑓 . As the effective nuclear charge (Zeff)—the positive
charge “felt” by an electron—increases, outer electrons are pulled closer to
the nucleus; thus, the atoms are smaller.
1. Down a group, n dominates. As we move down a main group, each
member has one more level of inner electrons that shield the outer
electrons very effectively. Even though calculations show Zeff on the
outer electrons rising moderately for each element in the group, the
atoms get larger as a result of the increasing n value. Atomic radius
generally increases in a group from top to bottom.
2. Across a period, Zeff dominates. As we move across a period of
main-group elements, electrons are added to the same outer level, so
the shielding by inner electrons does not change. Because outer
electrons shield each other poorly, Zeff on the outer electrons rises
significantly, and so they are pulled closer to the nucleus. Atomic
radius generally decreases in a period from left to right
Ionization energy (IE) is the energy (in kJ) required for the complete removal of
1 mol of electrons from 1 mol of gaseous atoms or ions (always positive).
Pulling an electron away from a nucleus
requires energy to overcome the attraction.

Ion+(g) → ion2+(g) + e- Δ E = IE2 (always > IE1)

Atoms with a low IE1 tend to form cations during reactions, whereas those with
a high IE1 (except the noble gases) often form anions.

There is a roughly inverse relationship between IE1 and atomic size: as size
decreases, it takes more energy to remove an electron.
1. Down a group. As we move down a main group, the orbital’s n value increases and
so does atomic size. As the distance from nucleus to outermost electron increases, the
attraction between them lessens, making the electron easier to remove. Ionization
energy generally decreases down a group.
2. Across a period. As we move left to right across a period, the orbital’s n
value stays the same, so Zeff increases and atomic size decreases. As a
result, the attraction between nucleus and outer electrons increases,
which makes an electron harder to remove. Ionization energy generally
increases across a period: it is easier to remove an outer electron from an
alkali metal than from a noble gas.
The electron affinity (EA) is the energy change (in kJ) accompanying the
addition of 1 mol of electrons to 1 mol of gaseous atoms or ions.

In most cases, energy is released when the first electron is

added because it is attracted to the atom’s nuclear charge.
Thus, EA1 is usually negative.
1. Reactive nonmetals. The elements in Group 6A(16) and especially
those in Group 7A(17) (halogens) have high ionization energies and
highly negative (exothermic) electron affinities. These elements lose
electrons with difficulty but attract them strongly. Therefore, in their
ionic compounds, they form negative ions.
2. Reactive metals. The elements in Groups 1A(1) and 2A(2) have low
ionization energies and slightly negative (exothermic) electron
affinities. In both groups, the elements lose electrons readily but
attract them only weakly, if at all. Therefore, in their ionic compounds,
they form positive ions.
3. Noble gases. The elements in Group 8A(18) have very high ionization
energies and slightly positive (endothermic) electron affinities.
Therefore, these elements tend not to lose or gain electrons. In fact,
only the larger members of the group (Kr, Xe, Rn) form any
compounds at all.
Relative Tendency to Lose Electrons
Because noble gases have high IEs and positive
(endothermic) EAs, they typically do not form ions but
remain chemically stable with a filled outer energy
level (ns2 np6 ). Elements in Groups 1A(1), 2A(2),
6A(16), and 7A(17) that readily form ions either lose
or gain electrons to attain a filled outer level and thus
a noble gas configuration. Their ions are said to be
isoelectronic (Greek iso, “same”) with the nearest
noble gas.
• electrons with the highest n value are removed first
• For main-group, s-block metals, remove all electrons with the highest n
value.
• For main-group, p-block metals, remove np electrons before ns
electrons.
• For transition (d-block) metals, remove ns electrons before (n - 1)d
electrons.
• For nonmetals, add electrons to the p orbitals of highest n value.
• A species with unpaired electrons exhibits paramagnetism: it is attracted
by an external magnetic field. A species with all electrons paired exhibits
diamagnetism: it is not attracted (and, in fact, is slightly repelled) by a
magnetic field.
Ionic Size vs. Atomic Size

• Cations are smaller than their parent atoms. When a cation forms,
electrons are removed from the outer level. The resulting decrease in
electron repulsions allows the nuclear charge to pull the remaining
electrons closer.
• Anions are larger than their parent atoms. When an anion forms,
electrons are added to the outer level. The increase in repulsions
causes the electrons to occupy more space.
• ionic size increases down a group because the number of energy levels
increases.
• across a period, however, the pattern is more complex. Size decreases
among the cations, then increases tremendously with the first of the
anions, and finally decreases again among the anions.
• When an element forms more than one cation, the greater the ionic
charge, the smaller the ionic radius.
To summarize:

• Ionic size increases down a group.

• Ionic size decreases across a period but increases from cations to
anions.
• Ionic size decreases with increasing positive (or decreasing negative)
charge in an isoelectronic series.
• Ionic size decreases as charge increases for different cations of a given
element.