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Atomic Theory:

The Quantum Model


of the Atom
Chapter 11

Review: the planetary model of the atom


(1911)
Every atom contains an extremely small, extremely dense
nucleus.
All of the positive charge and nearly all of the mass of an
atom are concentrated in the nucleus.
The nucleus is surrounded by a much larger volume of
nearly empty space that makes up the rest of the atom.
In the vast open space that comprises most of the volume
of an atom, electrons travel in circular orbits around the
nucleus

Limitations of the planetary model


First ionization Energy:
Energy required to
remove one electron from
a gaseous atom of an
element
The properties of the
elements do not change
smoothly as the atomic
number increases!

Limitations of the planetary model


Does not explain the different properties of
atoms in different groups (or chemical families)
Why are the noble gases so unreactive?
Why are they gases?

Why do metals conduct electricity?

Limitations of the planetary model


Does not allow us to understand or predict the way that
atoms will bond to create molecules
Why do the atoms of some elements tend to form anions,
while others form cations?
Cl-

Na+
Ca2+

Br-

Fe2+

Fe3+

Why do the atoms of the element oxygen tend to bond to


two others atoms (H2O), while carbon atoms make 4
bonds (CH4)?
And why dont the electrons spiral down into the nucleus?

Quantization of light
White light shone through a prism produces a continuous
spectrum

The Quantization of light


When an element is heated until it emits light and that
light passes through a prism, a line spectrum forms
The light only contains a few wavelengths - only waves
with specific energies

Each element has a unique line


spectrum
The line spectra of hydrogen, mercury, and neon
Each type of atom emits specific, but different, wavelengths
of light

Absorption and emission of light

Energy is absorbed as an electron is promoted from one


orbit to another
Energy (light) is emitted as the electron returns to its ground
state - an exact amount of energy corresponding to a
specific wavelength of light
The emission lines happen when heat excites the electrons,
which emit photons when they return to the ground state

What have we learned?


Only specific colors (wavelengths) of light are observed in
emission spectra
Energy is being emitted in specific amounts (quanta)
The electron orbitals have very specific energies
But so far we havent explained anything!
what about the pattern of ionization energies?
why do the elements have different chemical properties?
why dont electrons fall into the nucleus?

Max Planck made the math work by only allowing certain


specific energies to exist
the energies needed for electrons to traverse the last spiral into
the nucleus are not available to those electrons!

The Quantum concept

The Bohr model of the hydrogen atom


Proposed by Niels Bohr, a Danish scientist, in 1913.
Bohr took Plancks mathematical cheat and assumed it
was real
Electrons can only be in certain orbits

The Bohr model


Ground State: Lowest-energy orbit available
Excited States: Orbits with higher energy than the ground
state
Orbits in the Bohr model are called
Principal Energy Levels or
Principal Quantum Numbers (n)
Explains the line spectra and keeps the electrons away
from the nucleus, but leaves us with some questions
Why do the electrons only occupy certain orbits?
Why do elements have the properties we observe?

The quantum mechanical model of


the atom
de Broglie (1924): Matter in motion, such as electrons, has
properties that are normally associated with waves
mv = h/

m = mass
v = velocity
h = Planck constant
= wavelength

An electron traveling at one twentieth light speed has a


wavelength of 5 x 10-11 m - the radius of a hydrogen atom
A 50 kg person running at 10 m/sec has a wavelength of
1.3 x 10-36 m - which is not meaningful
Schrdinger (1925-28): Applied the principles of wave
mechanics to atoms

Wave mechanics
The vibration of a constrained string (a guitar string is attached
at the bridge and the nut) has certain natural frequencies
(harmonics) that are integer multiples of the fundamental
The same is true for an electron behaving as a wave,
constrained by the potential well of the nucleus

Suggests that electrons are particles,


in specific locations.
Heisenberg (1925-1927) showed that
this was not a meaningful model due
to uncertainty in the speeds and
positions of the electrons.

Suggests that electrons are waves.


Orbitals are interpreted as
probability densities.
Electrons are fuzzy clouds of
charge.

Solutions to the Schrodinger equation


for the hydrogen atom
Orbitals

Region in space
around a nucleus in
which there is a
high probability of
finding an electron
Each orbital can be
occupied by 0, 1 or
2 electrons

Quantum numbers
The quantum mechanical description of each electron in
in a multi-electron atom can be described using four
quantum numbers
For each electron there is a unique set of quantum
numbers
The quantum numbers describe the energy level and
probable location of the electron

Principal Energy Levels, n


n = 1,2,3,4,5,6,7
Generally, energy increases with increasing n
Distance of the electron from the nucleus increases
with increasing n

(Remember the
Bohr orbits)

Sublevels and Orbitals


For each principal energy level there are one or more
sublevels (s, p, d, f) associated with different types of orbital
The total number of sublevels is equal to n, the principal
quantum number
Principal quantum number = 1
The lowest energy level
Just one solution to the
Schrodinger equation,
One sublevel, s
One orbital, which can
contain a maximum of two
electrons
If your atom only contains
two electrons they are likely
to be in this region of space

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Sublevels and Orbitals


For each principal energy level there are one or more
sublevels (s, p, d, f) associated with different types of orbital
The total number of sublevels is equal to n, the principal
quantum number
Principal quantum number
(principal energy level) = 2

Two sublevels, s and p


One orbital in the s sublevel
and three in the p sublevel
Each orbital can contain a
maximum of two electrons
Maximum electrons at this
principle energy level = 8

Sublevels and Orbitals


For each principal energy level there are one or more
sublevels (s, p, d, f) associated with different types of orbital
The total number of sublevels is equal to n, the principal
quantum number

Principal quantum number = 3

Three sublevels: s, p and d


One orbital in the s sublevel,
three in the p sublevel, 5 in
the d sublevel
Each orbital can contain a
maximum of two electrons
for a total of 18 electrons
HOWEVER! The energy of
the 4s sublevel is less than
the 3d

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Sublevel energy level order:


1s < 2s < 2p < 3s < 3p <
4s < 3d < 4p < 5s < 4d <
5p < 6s < 4f < 5d < 6p <
7s < 5f < 6d
You can memorize this sequence or.

This chart, or..

Each box can hold


0, 1 or 2 electrons

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Remember the pattern from the periodic table

The electron configurations

Hydrogen has only one electron. It is in the 1s orbital (the lowest


energy orbital)
Helium has two electrons, they can both go into the 1s orbital
Lithium has three electrons, so two go in the 1s orbital and one
goes into the 2s orbital
Carbon has 6 electrons, 2 in the 1s orbital, 2 in the 2s orbital and
2 in the 2p orbital

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Summary
Principal energy level
n = 1, 2, 3, 4, 5, 6, 7

Sublevel
s, p, d, f

Number of orbitals
s: 1, p: 3, d: 5, f: 7

Orbital occupancy, number of electrons in orbital


limited to 2

Rules for writing electron


configurations
1. Electrons occupy the lowest
energy sublevel available

2. No more than two electrons


can occupy any one orbital

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Example: Electron configuration for Al


Write the electron
.
configuration of
aluminum
Step 1: Locate Al in the
periodic table
The atomic number is
13 (13 protons) so we
must have 13 electrons
in the neutral atom

Example: Electron configuration for Al


Step 2: follow the periodic table to list all sublevels in order of
increasing energy until you get to the block in which the element
is located
This gives the energy levels and orbitals which will be occupied

1s 2s 2p 3s 3p

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1s 2s 2p 3s 3p
Step 3: Add the appropriate number of
electrons to each sublevel until all 13 are used
1s2 2s2 2p6 3s2 3p1

Step 4: Check for the correct


number of electrons
2 + 2 + 6 + 2 + 1 = 13 = Z for Al

Example: Electron configuration for C


The atomic number
is 6
.
(6 protons) so we must
have 6 electrons in the
neutral atom
1s 2s 2p
1s2 2s2 2p2

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Noble gas cores


The noble gases (last column of the periodic
table) are very stable
All the orbitals within one principle energy level
are filled
Electrons are not likely to leave these energy
levels (for example, to form a bond with
another atom - the noble gases are very
unreactive!)
For elements beyond Neon (Ne) the innermost
electrons form an unreactive noble gas core

A noble-gas core is commonly used


when writing electron configurations
Al:

1s22s22p63s23p1
Ne

Al:

[Ne]3s23p1

Since the n = 1 and 2 electrons are in the inner part of the


atom and therefore not involved in bonding, we dont
need much detail about their configurations

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Writing electron configurations


using noble gas cores
1. Find the highest atomic-numbered noble gas (Group
8A element) less than the atomic number of the
element for which the configuration is being written
2. Write the elemental symbol of the noble gas in square
brackets, followed by the remaining configuration (the
valence electrons)

Example: Electron configuration for Ni


The atomic number is
28
.
We have 28 electrons
in the neutral atom
Sublevels:
1s 2s 2p 3s 3p 4s 3d
Orbital occupancy:
1s2 2s2 2p6 3s2 3p6 4s2
3d8
[Ar] 4s2 3d8

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The quantum model of an atom:


Does it work?
Does it explain (and predict!)
experimentally observed
behavior?
Example: trends in ionization
energies (energy required to
remove an electron from an atom
leaving behind a charged ion)

Note two periodic trends in ionization energy:


1. Energy decreases down a group
2. Energy increases across a period

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Explaining the trends in ionization


energies
1. Energy decreases down a group
Atoms are larger further down the table (more electrons,
larger principle quantum numbers)
The negative electrons in the outermost orbitals are
further from the positive nucleus
The electrostatic force holding them into the atom is less

Explaining the trends in ionization


energies
2. Energy increases across a period (and
zig-zags)
Removing one electron from Li, Na, K leaves a noble gas
structure (very stable) and so is relatively easy

Removing one electron from Be or Mg is a little harder,


but from B or Al leaves a filled s orbital (relatively stable)
Ionization energy increases as the energy level fills and
the atom becomes more stable

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Average size of atoms


Note two periodic
trends in atomic size:
1.Size increases down
a group
2.Size decreases
across a period

Why?
1. Down a group:
The average distance of the outermost electron
increases with increasing n, so atoms become bigger

2. Across a period:
Nuclear charge increases, holding the electron more tightly,
and the principal energy level of the outermost electron
remains the same, so atoms become smaller

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The quantum model of an atom:


does it work?
The orbital model of an atom failed to explain the
periodic behavior observed by Mendeleev
Does this new model do better?
Yes, because all the elements with the same
valence electron configuration are grouped
together
These elements have similar properties
(chemical families)

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