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1. ATOMIC THEORY
2. IONIC BONDING
3. COVALENT BONDING
4. SPECTROSCOPY
5. SPECIAL TOPICS
Dr. Akhmad Syoufian
Department of Chemistry
Faculty of Mathematics and Natural Sciences
Gadjah Mada University
ATOMIC THEORY
Dr. Akhmad Syoufian
Department of Chemistry
Faculty of Mathematics and Natural Sciences
Gadjah Mada University
Modern atomic theory:
In the early years of the 19th century, John Dalton
developed his atomic theory in which he proposed
that each chemical element is composed of atoms
of a single, unique type, and that though they are
both immutable and indestructible, they can
combine to form more complex structures (chemical
compounds). How precisely Dalton arrived at his
theory is not entirely clear, but nonetheless it
allowed him to explain various new discoveries in
chemistry that he and his contemporaries made.
Modern atomic theory (continued):
Atoms were thought to be the smallest possible
division of matter until 1897 when J.J. Thomson
discovered the electron through his work on
cathode rays. He thus concluded that atoms were
divisible, and that the corpuscles (they would later
be renamed electrons by other scientists) were their
building blocks. To explain the overall neutral
charge of the atom, he proposed that the
corpuscles were distributed in a uniform sea or
cloud of positive charge; this was the plum pudding
model
Modern atomic theory (continued):
Thomson's plum pudding model was disproved in
1909 by one of his students, Ernest Rutherford,
who discovered that most of the mass and positive
charge of an atom is concentrated in a very small
fraction of its volume, which he assumed to be at
the very center.
Modern atomic theory (continued):
The gold foil experiment
Top: Expected results: alpha
particles passing through
the plum pudding model of
the atom with negligible
deflection.
Bottom: Observed results: a
small portion of the
particles were deflected,
indicating a small,
concentrated positive
charge.
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Modern atomic theory (continued):
Quantum theory revolutionized physics at the
beginning of the 20th century, when Max Planck
and Albert Einstein postulated that light energy is
emitted or absorbed in discrete amounts known as
quanta (singular, quantum).
In 1913, Niels Bohr incorporated this idea into his
Bohr model of the atom, in which the electrons
could only orbit the nucleus in particular circular
orbits with fixed angular momentum and energy,
their distances from the nucleus being proportional
to their respective energies.
Modern atomic theory (continued):
The Bohr model of the atom;
Under this model electrons
could not spiral into the
nucleus because they could
not lose energy in a
continuous manner; instead,
they could only make
instantaneous "quantum
leaps" between the fixed
energy levels. When this
occurred, light was emitted
or absorbed at a frequency
proportional to the change
in energy.
Modern atomic theory (continued):
Bohr's model was only able to predict the spectral
lines of hydrogen; it couldn't predict those of multi-
electron atoms. Worse still, as spectrographic
technology improved, additional spectral lines in
hydrogen were observed which Bohr's model
couldn't explain.
In 1916, Arnold Sommerfeld added elliptical orbits
to the Bohr model to explain the extra emission
lines, but this made the model very difficult to use,
and it still couldn't explain complex atoms.
Modern atomic theory (continued):
In 1924, Louis de Broglie proposed that all moving
particles-particularly subatomic particles such as
electrons-exhibit a degree of wave-like behavior.
Erwin Schrdinger, fascinated by this idea, explored
whether or not the movement of an electron in an
atom could be better explained as a wave rather
than as a particle.
Schrdinger's equation, published in 1926,
describes an electron as a wave-function instead of
as a point particle, and it elegantly predicted many
of the spectral phenomena Bohr's model failed to
explain.
Modern atomic theory (continued):
The five atomic orbitals of a neon atom, separated and
arranged in order of increasing energy from left to right,
with the last three orbitals being equal in energy. Each
orbital holds up to two electrons, which exist for most of
the time in the zones represented by the colored
bubbles. Each electron is equally in both orbital zones,
shown here by color only to highlight the different wave
phase.
Modern atomic theory (continued):
Since a wave-function incorporates time as well as
position, it is impossible to simultaneously derive
precise values for both the position and momentum
of a particle for any given point in time; this became
known as the uncertainty principle.
This invalidated Bohr's model, with its neat, clearly
defined circular orbits.
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Modern atomic theory (continued):
The modern model of the atom describes the
positions of electrons in an atom in terms of
probabilities. An electron can potentially be found at
any distance from the nucleus, but - depending on
its energy level - tends to exist more frequently in
certain regions around the nucleus than others; this
pattern is referred to as its atomic orbital.
THANK YOU FOR YOUR ATTENDANCE
@ 2008
Department of Chemistry
Faculty of Mathematics and Natural Sciences
Gadjah Mada University
ENERGIES AND ORBITALS IN MANY-
ELECTRON ATOMS
Dr. Akhmad Syoufian
Department of Chemistry
Faculty of Mathematics and Natural Sciences
Gadjah Mada University
Many-Electron Atoms: The First Two Rules:
The quantum state of an electron is specified by the
orbital quantum numbers, n, l, and m, plus an
electron spin quantum number s. So far we have
neglected this property of electrons, and we will not
say any more about it at this stage except to note
that scan have one of two values, + or -.
The Pauli Exclusion Principle says that no two
electrons in an atom may have be in the same
quantum state.
Many-Electron Atoms: The First Two Rules:
That is, no two electrons can have the same four
quantum numbers, n, l, m, and s.
This is equivalent to saying that no orbital (specified
by n, l, and m) can be occupied by more than two
electrons.
The second rule is that electrons in atoms (and
molecules) generally exist in their lowest possible
energy state. This is called the ground state.
This is enough to begin to handle multi-electron atoms,
at least He.
Worked Example: The Ground State
Electronic Configuration of He:
Using the atomic orbitals obtained for the hydrogen atom, we
fill orbitals beginning with the lowest energy. (To do this we
are pretty much ignoring the interactions between electrons,
and treating them as two independent waves bound to the
same (2+) nucleus.)
Electron 1 goes into the 1s orbital (n=1, l=0, m=0) with s =
+
Electron 2 goes into the 1s orbital (n=1, l=0, m=0) with s = -

The ground state electron configuration of He is written as

1s
2
. (For H it is written 1s
1
.)
What happens to the next electron?
What is the ground state configuration of Li?
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Filling the n = 2 orbitals: Rule 3:
After He, the n=1 (1s) orbital is full. According to the wave
equation for the hydrogen atom, the 2s and three 2p orbitals
all have the same energy, so the next electron could go into
any of the four n=2 orbitals.
However we have already seen that the wave-functions for
the s and p orbitals are different.
s orbitals have their maximum amplitude at the nucleus. This
means that electrons in s orbitals are bound by the true
nuclear charge (3+ for Li, etc.)
p orbitals have a node at the nucleus. Their interaction with
the nucleus is screened by electrons closer in, so electrons
in 2p orbitals are bound by a lower effective charge.
Filling the n = 2 orbitals: Rule 3:
The different effective nuclear charges lower the energy of the
ns orbital relative to np, so the s orbital fills first with up to 2
electrons. The ground state configuration of Li is 1s
2
2s
1
, and for
Be it is 1s
2
2s
2
.
Filling the n = 2 orbitals: Rule 4:
After Be, the 1s and 2s orbitals are full. The 2p orbitals are
next to fill.
Three 2p orbitals can accommodate a total of six electrons,
which gives the configurations of elements B through to Ne.
Filling the n = 2 orbitals: Rule 4:
This is summarized in Hunds Rule, that the lowest
energy electron configuration in orbitals of equal
energy is the one with the maximum number of
unpaired electrons with parallel spins.
Hunds Rule:
Electron configurations are often represented in an orbital
diagram, which explicitly shows the number and spin of
electrons in various atomic orbitals.
Filling higher orbitals:
The same rules apply for the order of orbital filling as we
deduced for n=2. First the 3s orbitals fill (Na & Mg), and
then 3p (Al-Ar).
As the angular momentum quantum number, l, increases,
the orbitals extend further from the nucleus, and all orbitals
except s have nodes at the nucleus. This means that the
energy of an orbital increases with l for a given n.
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Filling higher orbitals:
This effect is big enough that
the energy of the 4s orbital is
lower than 3d. The order of
increasing energies and of
filling is shown in the diagram
at right.
An important consequence of this is in
atomic spectroscopy is that of the
energy level spacing or differences E
are unique to each atom, which means
that we can identify atoms by their
atomic absorbance or emission spectra.
Multi-Electron Configurations:
Pauli Exclusion Principle.
No two electrons in an
atom may be in the same
quantum state {n, l, m, s}
Aufbau Principle. Electrons
adopt the lowest possible
energy configuration.
Penetration. Orbitals of
equal n nearest the
nucleus have lowest
energy: s< p< d< f
Hunds Rule. Maximise
unpaired electron spins in
degenerate orbitals.
Orbitals table: Worked example: Multi-Electron
Configurations:
What are the electron configurations of atomic Ca and Ge?
Ca has 20 electrons, which we fill as follows
1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
or [Ar]4s
2
Ge has 32 electrons, which we fill as follows
1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
4p
2
or [Ar]4s
2
3d
10
4p
2
Multi-Electron Configurations:
Orbitals with the same principal quantum number but different
azimuthal quantum numbers have different energies in multi-
electron atoms.
? What gives
Orbitals and Electron Shells:
Periodic trends are related to electron configurations. The
classical model of the atom included the concept of electron
shells derived from the row lengths in the periodic table.
Noble gases are unreactive because they contain filled
electron shells. This emerges from quantum theory as a
natural consequence of the allowed orbital structure.
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Structure of the Periodic Table:
Atoms with the same outer shell configuration are expected
to have similar chemical properties. Outer shell or valence
electrons are important in the formation of chemical bonds
(as we shall see later). They will lie in the same group in the
periodic table, and form compounds with the same
stoichiometry.
Structure of the Periodic Table:
The periodic table can be regarded in terms of electron
configurations, denoted by orbital angular momentum
quantum number. The periodic table may thus be divided
into s, p, d, and f blocks according to which orbital is being
filled.
THANK YOU FOR YOUR ATTENDANCE
@ 2008
Department of Chemistry
Faculty of Mathematics and Natural Sciences
Gadjah Mada University
PERIODIC ATOMIC PROPERTIES AND
QUANTUM THEORY
Dr. Akhmad Syoufian
Department of Chemistry
Faculty of Mathematics and Natural Sciences
Gadjah Mada University
1. Atomic Radius:
The atomic radius is determined by the electronic
configuration, and particularly by how far the electron
density extends from the nucleus. The wave-functions and
potential energy help make sense of the observed trends.
1. Atomic Radius (continued):
Radius increases down
a group as electrons
add to new shells.
Across a row the radius
decreases as the
nuclear charge
increases.
From group 8 (noble
gas) to the group 1
(alkali metal). The one
additional electron goes
into the next s-orbital,
increasing the radius
markedly.
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1. Atomic Radius (continued): 2. Ionization Energy:
Ionization energy is related to the energy required to remove
an electron from an atom.
Clearly a multi-electron atom would have many ionization
energies. So by definition the first ionization energy is
defined as the energy required to remove the outer most
electron from a neutral atom in the gas phase.
Quantum theory also helps make sense of ionization energy
trends.
2. Ionization Energy (continued):
Stepping down a group,
the outer electrons of
each element is another
shell further away from
the nucleus. Inner
electrons screen the
nuclear attraction that
binds the electron, so
ionization becomes
easier.
Across a row, electrons are added to the same shell. The
increase in nuclear charge without additional screening
holds the electrons more tightly to the nucleus.
2. Ionization Energy (continued):
The figure below shows the 1st ionization energies.
Take look more closely! At the trend in ionization energies we
see two deviations. Boron's ionization energy is lower than
beryllium's and oxygen's is lower than nitrogen's.
What gives ?
3. Electron Affinity:
Electron affinity is the energy change associated with the
addition of an electron to a neutral atom in the gas phase to
form the single charged anion.
Except for Group 2 and Noble Gases which have filled sub-
shells, forming the anion is exothermic - i.e. EA is negative.
The halides have the largest electron affinity with the
greatest amount of energy released on anion formation.
In general, the size of the energy change (+ or -) decreases
as you go down the group.
3. Electron Affinity (continued):
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3. Electron Affinity (continued):
Fluorine (atomic number 9) has a very negative electron
affinity, energy is released when is gains an electron.
Meanwhile, lithium and beryllium do not want to gain
electrons. Beryllium is particularly uninterested.
? What gives
THANK YOU FOR YOUR ATTENDANCE
@ 2008
Department of Chemistry
Faculty of Mathematics and Natural Sciences
Gadjah Mada University