DR.
AHMED ATEF
01017577386
CHAPTER 7
ATOMIC STRUCTURE
AND PERIODICITY
Chemistry Course
Grade 12
STEM
DR/ Ahmed Atef 01017577386
Quantum Numbers
Quantum numbers are required to describe the distribution of electron density in
an atom.
There are three quantum numbers necessary to describe an atomic orbital.
• The principal quantum number (n) – designates size and energy of the
orbital
• The angular moment quantum number (l) – describes the shape of the
orbital
• The magnetic quantum number (ml) – specifies orientation of the orbital
in the space.
• The principal quantum number (n) designates the size of the orbital.
• Larger values of n correspond to larger orbitals.
• The allowed values of n are integral numbers: 1, 2, 3 and so forth.
• The angular moment quantum number (l) describes the shape of the orbital.
• The values of l are integers that depend on the value of the principal
quantum number
• The allowed values of l range from 0 to n – 1.
• The magnetic quantum number (ml) describes the orientation of the orbital
in space.
• The values of ml are integers that depend on the value of the angular
moment quantum number: (– l,…0,…+l)
Example: If n = 2, l can be 0 or 1.
l 0 1 2 3
Orbital designation s p d f
NOTE
• A collection of orbitals with the same value of n is frequently called a
shell.
• A collection of orbitals with the same value of n and l is referred to as a
subshell.
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Allowed values of the quantum numbers n, l, ml
When n is l can be When l is ml can be
1 Only 0 0 Only 0
0 Only 0
2 0 or 1 1 -1 , 0 , +1
0 Only 0
3 0,1 or 2 1 -1 , 0 , +1
2 -2 , -1 , 0 , +1 , +2
0 Only 0
4 0,1,2, or 3 1 -1 , 0 , +1
2 -2 , -1 , 0 , +1 , +2
3 -3 , -2 , -1 , 0 , +1 , +2 , +3
Quantum numbers designate shells, subshells, and
orbitals:
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Example
• What are the possible values for the magnetic quantum number (ml) when
the principal quantum number (n) is 3 and the angular quantum number
(l) is 1?
Strategy Recall that the possible values of ml depend on the value of l, not on
the value of n.
Setup The possible values of ml are – l,…0,…+l.
Solution The possible values of ml are -1, 0, and +1.
• The electron spin quantum number (ms ) is used to specify an electron’s
spin.
• There are two possible directions of spin.
• Allowed values of ms are +½ and −½.
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• A beam of atoms is split by a magnetic field.
• Statistically, half of the electrons spin clockwise, the other half spin
counterclockwise.
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Atomic orbitals
All s orbitals are spherical in shape but differ in size: 1s < 2s < 3s
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Example
• List the values of n, l, and ml for each of the orbitals in a 4d subshell.
Strategy Consider the significance of the number and the letter in the 4d
designation and determine the values of n and l. There are multiple values for
ml, which will have to be deduced from the value of l.
Setup The integer at the beginning of the orbital designation is the principal
quantum number (n). The letter in an orbital designation gives the value of the
angular momentum quantum number (l). The magnetic quantum number (ml)
can have integral values of – l,…0,…+l.
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Electron configurations
• The electron configuration describes how the electrons are distributed in
the various atomic orbitals.
• In a ground state hydrogen atom, the electron is found in the 1s orbital.
• If hydrogen’s electron is found in a higher energy orbital, the atom is in
an excited state.
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• In a multi-electron atom, the energies of the atomic orbitals are split.
• According to the Pauli exclusion principle, no two electrons in an atom
can have the same four quantum numbers.
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• The Aufbau principle states that electrons are added to the lowest energy
orbitals first before moving to higher energy orbitals.
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• According to Hund’s rule, the most stable arrangement of electrons is the
one in which the number of electrons with the same spin is maximized.
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General rules for writing electron configurations:
1. Electrons will reside in the available orbitals of
the lowest possible energy.
2. Each orbital can accommodate a maximum of
two electrons.
3. Electrons will not pair in degenerate orbitals if an
empty orbital is available.
4. Orbitals will fill in the order indicated in the
figure.
Example:
• Write the electron configuration and give the orbital diagram of a calcium
(Ca) atom (Z = 20).
Setup Because Z = 20, Ca has 20 electrons. They will
fill in according to the diagram at right. Each s subshell
can contain a maximum of two electrons, whereas each p
subshell can contain a maximum of six electrons.
• Remember that the 4s orbital fills before the 3d orbitals.
Notes:
• Ground state: is the lowest energy, most stable arrangement.
• Exited state: a state of a physical system that is higher in energy than the
ground state.
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Electron Configurations and the Periodic Table
• The electron configurations of all elements except hydrogen and helium can
be represented using a noble gas core.
• The electron configuration of potassium (Z = 19) is 1s 22s22p63s23p64s1.
• Because 1s22s22p63s23p6 is the electron configuration of argon, we can
simplify potassium’s to [Ar]4s1.
• Elements in Group 3B through Group 1B are the transition metals.
• Following lanthanum (La), there is a gap where the lanthanide (rare
earth) series belongs.
• After actinium (Ac) comes the actinide series.
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There are several notable exceptions to the order of electron filling for some
of the transition metals.
• Chromium (Z = 24) is [Ar]4s13d5 and not [Ar]4s23d4 as expected.
• Copper (Z = 29) is [Ar]4s13d10 and not [Ar]4s23d9 as expected.
The reason for these anomalies is the slightly greater stability of d subshells
that are either half-filled (d5) or completely filled (d10).
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Example:
• Write the electron configuration for an arsenic atom (Z = 33) in the
ground state.
Setup The noble gas core for As is [Ar], where Z = 18
for Ar.
The order of filling beyond the noble gas core is 4s, 3d,
and 4p. Fifteen electrons go into these subshells because
there are 33 – 18 = 15 electrons in As beyond its noble
gas core.
• Arsenic is a p-block element; therefore, we should expect its outermost
electrons to reside in a p subshell.
Notes:
Atomic number: represents the number of protons in the nucleus of all atoms,
isotopes, and ions of the element.
Mass number: is the total number of nucleons in the nucleus of an atom, isotope,
or ion.
Trends & the Periodic Table
• More than 20 properties change in predictable way-based location of
elements on Periodic table.
• Some properties:
1. Density.
2. Melting point / Boiling point.
3. Atomic radius.
4. Ionization energy.
5. Electronegativity.
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Atomic Radius
Atomic radius: defined as ½ distance between neighbouring nuclei in
molecule or crystal
• Affected by
1. Number of energy levels
2. Proton Pulling Power
• Cs has more energy levels, so it’s bigger.
• As we go across, elements gain electrons,
but they are getting smaller.
Why does this happen??
• As you go from left to right, you gain more protons (the atomic number
increases).
• You have greater “proton pulling power”.
Remember the nucleus is + ve and the electrons are - ve so they get pulled
towards the nucleus.
• The more protons you have, the more Proton Pulling Power.
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Electron Configuration of Compounds
• When two nonmetals react to form a covalent bond, they share electrons in
a way that completes the valence electron configurations of both atoms. That
is, both nonmetals attain noble gas electron configurations.
• When a nonmetal and a representative-group metal react to form a binary
ionic compound, the ions form so that the valence electron configuration of
the nonmetal achieves the electron configuration of the next noble gas atom
and the valence orbitals of the metal are emptied. In this way both ions achieve
noble gas electron configurations.
Ionic size
• Various factors influence ionic size. We will first consider the relative sizes
of an ion and its parent atom. Since a positive ion is formed by removing one
or more electrons from a neutral atom, the resulting cation is smaller than its
parent atom. The opposite is true for negative ions; the addition of electrons
to a neutral atom produces an anion significantly larger than its parent atom.
• It is also important to know how the sizes of ions vary depending on the
positions of the parent elements in the periodic table. The figure below
shows the sizes of the most important ions (each with a noble gas
configuration) and their position in the periodic table. Note that ion size
increases down a group. The changes that occur horizontally are complicated
because of the change from predominantly metals on the left-hand side of
the periodic table to nonmetals on the right-hand side. A given period thus
contains both elements that give up electrons to form cations and ones that
accept electrons to form anions.
• One trend worth noting involves the relative sizes of a set of isoelectronic
ions “ions containing the same number of electrons”. Consider the ions O2- ,
F- , Na+ ,Mg2+ , and A13+. Each of these ions has the neon electron
configuration. How do the sizes of these ions vary? In general, there are two
important facts to consider in predicting the relative sizes of ions: the number
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of electrons and the number of protons. Since these ions are isoelectronic, the
number of electrons is 10 in each case. Electron repulsions
• Therefore, should be about the same in all cases. However, the number of
protons increases from 8 to 13 as we go from the O2- ion to the A13+ ion. Thus,
in going from O2- to A13+, the 10 electrons experience a greater attraction as
the positive charge on the nucleus increases. This causes the ions to become
smaller. You can confirm this by looking at the Figure below. In general, for
a series of isoelectronic ions, the size decreases as the nuclear charge Z
increases.
Examples
Relative Ion Size I
• Arrange the ions Se2- , Br -, Rh+, and Sr2+ in order of decreasing size.
Relative Ion Size II
• Choose the largest ion in each of the following groups.
a. Li+, Na+, K+, Rb+, Cs+.
b. Ba2+ , Cs+ , I- , Te2-.
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Ionization Energy
The amount of energy required to remove a valence electron from an atom
in gas phase.
• 1st ionization energy = energy required to remove the most loosely held
valence electron (e- farthest from nucleus).
• Cs valence electron lot farther away from nucleus than Li.
• Electrostatic attraction much
weaker so easier to steal electron
away from Cs.
• THEREFORE, Li has a higher
Ionization energy then Cs.
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Electronegativity
The ability of atom to attract electrons in bond.
• Noble gases tend not to form bonds, so don’t have electronegativity
values.
• The measuring scale = Pauling scale.
• Fluorine: most electronegative element = 4.0 Pauling.
Electron affinity
The ability of an atom to accept an electron.
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