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v: number of wavelengths passing a point in 1 second
Light is electromagnetic radiation
There are many kinds of light together they make up the
Electromagnetic Spectrum:
All of the above are forms of wave motion:
observer
28
Electromagnetic radiation (light) and energy
c = v
speed of light: a constant
short
wavelength
high
frequency
E = hv
Plank's Constant
short
wavelength
high
frequency
or
high
energy
This explains why we worry about -rays (v high) and not about
microwaves (v low)
At times light also behaves as though it was made up of small
packets of energy. These are called photons
29
1890s Spectra for the light produced by cathode ray tubes
cathode
ray tube
gas at low
pressure
violet
high
energy
red
low
energy
very high
voltage
narrow
slit
Instead of a continuous spread of colours, the spectrum consists of families
of coloured lines which become closer together at higher frequency/shorter
wavelength/higher energy. Different gases give different patterns.
30
The big question is how do atoms, for example the atoms of gas in the cathode
ray tube, produce light in this way
The spectrum produced by sulfur atoms is shown below (ignore background
colours):
31
Jigsaw Piece 3: 1911 Ernest Rutherfords experiment with o-
particles and gold foil
o-Particles (alpha particles): produced by atoms undergoing radioactive
decay. They have a positive charge and are ejected by the atom at enormous
speeds (~ 15,000 km s
-1
). They are in fact the nuclei of helium atoms (see
below).
Gold foil: metals are malleable they can be hammered out into thin foils
only a few hundred atoms thick
Rutherfords experiment: as part of an investigation of the behaviour of o-
particles and of the structure of matter, he fired a beam of the particles at the
gold foil.
32
Ernest Rutherford
1871-1937
1871 Born in New Zealand
1894 Comes to Cambridge to
complete studies
1907 Professor of Physics in
the University of Manchester
1908 Nobel Prize for Chemistry
1919 Succeeds J. J. Thomson
as Professor of Physics in
Cambridge (Cavendish
Laboratory)
1937 Dies and is buried in
Westminster Abbey beside
Isaac Newton
33
detector
gold
foil
source of
o-particles
beam of
o-particles
The experiment and its results
99% of the o-
particles passed
straight through
Simulation:
www.mhhe.com/physsci/chemistry/essentialchemistry/flash/ruther14.swf
34
He had expected 100% of the particles to pass straight through:
because of the nature of the gold foil and the -particles, the experiment
was compared to firing artillery shells at tissue paper!!
100% pass
straight through
no nett electrostatic
force on positively
charged o-particles
because Thomson had proposed that matter (eg the gold foil) had a
plum pudding structure with electrons and protons distributed at
random.
What had Rutherford expected?
35
Rutherfords conclusions
All the positive particles (and the neutrons) are gathered together in
a very small nucleus surrounded by orbiting electrons. Only the very
small number of -particles that go close to the nucleus are deflected
the rest go straight through
orbiting
electron
nucleus (protons
and neutrons)
o-particles
o-particles
o-particles
o-particles
Coulombs
Law is an
inverse
square law of
force
F
q
1
q
2
r
2
36
Problem with Rutherfords simple nuclear model
Rutherfords nuclear model was a great step forward However because
of what was known about electromagnetic theory, it was immediately
realised that there was a problem
+
-
+
-
Theory says that a moving charge
should lose energy. If so the
electron should spiral down into
the nucleus. The simple
Rutherford atom is thus unstable
Atoms are stable and so the
electron should remain
spinning around the nucleus
37
The Year 1900
Information about the structure of an atom was
like a set of jigsaw pieces wait to be put together
The structure
of an atom
Concept of an atom
reintroduced by John
Dalton
Discovery of
sub-atomic
particles
Phenomenon of
spectra:
absorption and
emission of light by
matter
Rutherford's
experiment with gold
foil and
alpha particles
38
Key Points
1. Rutherfords nuclear model is basically correct
Electron
orbit
Electron
energy
level
Bohrs Model of the Structure of an Atom (1913)
2. Electrons orbiting the nucleus can occupy a number of
different orbits with different energies
3. Electrons are restricted to these energy values and cant have in
between values in other words the energy of electrons in an
atom is quantised. As long as an electron has one of these
energy levels, it does not fall into the nucleus
4. Electrons can move between energy levels, giving out or taking in
energy and thus explaining the phenomenon of spectra.
39
1885-1962
1
2
3
E
3
E
1
= E
1,3
= h
1,3
upper case
delta:
change or
difference
frequency or
colour of the
light given out
when electron
moves from
Level 3 down
to Level 1
The higher energy levels
are closer together than
those close to the nucleus
Schematic diagram of an atom
energy released as a
little packet of light
energy (photon)
nucleus
electron
orbits or
energy
levels
energy required occurs when the
electron absorbs a photon of light
E
1
< E
2
< E
3
40
1. Newtons rainbow spectrum: The sun has lots of different types of
atomic species each giving out different coloured light. This gives the
continuous spectrum we associate with sunlight.
2. Fraunhofers dark lines: Atomic
species in the suns atmosphere
absorb photons of a particular colour
(wavelength/frequency). These
missing photons are responsible for
the dark lines in the suns continuous
spectrum
sun
sun's
atmosphere
Using the Bohr model to the explain the origin of spectra
41
When the size of the transitions
is small, there is a large
difference between one
transition and the next.
However as the size of the
transitions increases, the
difference between successive
transitions becomes smaller
1
2
3
4
5
Family 1
Family 2
red: low E violet: high E
3. Spectra produced by cathode ray tubes: the pattern of lines in a family
getting closer together as we go towards the blue/violet (high energy) end
of the spectrum, is due to the fact that the energy levels available to the
electrons get closer together as we move away from the nucleus.
Family of transitions giving a family
of spectral lines
42
The concept of an orbital
Things are not as clear cut as it seemed at first
1900 Relativity (Einstein)
1924 Dual character (wave and particle) of small particles such as
electrons (de Broglie)
1927 Uncertainty Principle the momentum (p, mass x velocity) and
position (x) of a particle cannot both be known exactly (Heisenberg)
Orbital This replaces the concept of an orbit: a volume of space (3-D)
around a nucleus in which an electron is probably found or a volume of
space around a nucleus in which an electron spends most of its time
(uncertainty in p).(uncertainty in x) constant
orbital orbit
Orbit Fixed 2-D path (position) for an electron of definite mass: this
violates Uncertainty Principle and has to go.
43
Louis-Victor-
Pierre-
Raymond, 7th
duc de Broglie
1892-1987
Developing the Bohr Model of the Atom
1. A particular energy level is associated with a particular orbital
n = 1, 2, 3, 4.n
5. In practical terms the PQN tells us about the size of an orbital
2. A spectral line requires two energy levels (orbitals) and so the more
spectral lines we observe, the more energy levels are available
3. Numbers (or letters), known as quantum numbers, are used to label an
energy level (orbital)
4. The Principal Energy Levels are labelled using the Principal Quantum
Number (PQN), n:
44
6. If we examine the spectrum given by a particular element with very
good equipment, we find that some lines are split into a set of lines
very close together. As there are more lines than might be expected,
this means that there are more energy levels available to the electron
than expected => some Principal Energy Levels are made up of a
set of Sub-energy Levels.
n = 1 => l = 0 => no sub-levels
n = 2 => l = 0, 1 => 2 sub-levels
n = 3 => l = 0, 1, 2 => 3 sub-levels
n = 4 => l = 0, 1, 2, 3 => 4 sub-levels
More usual
labels
s
p
d
f
7. Sub-energy Levels are labelled using a Secondary Quantum
Number (SQN), l, where l = 0, 1, 2..n-1
45
8. This means for example that the 3
rd
Principal Energy Level is
actually a set of three energy levels.
Principal
Energy
Level 3
3d
3p
3s
7. In practical terms the SQN gives us the shape of the orbital
46
9. When an atom is placed in a magnetic field, some of the lines in its
spectrum separate into groups of lines. In other words there are still
further options in terms of energy levels. The number of energy
levels/orbitals in a particular group depends on the Sub-energy Level
involved and the levels are labelled using the Magnetic Quantum
Number (MQN), m
l
, where m
l
= -l,0,...+l (l = SQN)
s (l = 0) => m
l
= 0 => a single value and
so there is just one s level
p (l = 1) => m
l
= -1, 0, 1 => three p levels
More usual
labels
p
x
p
y
p
z
d: five levels
f: seven levels
47
10. In practical terms the MQN gives us the orientation of the orbital:
p
x
p
y
p
z
Note: In this course we will only be concerned with the shape and
orientation of the s and p orbitals
48
Overall energy level/orbital picture
The complete pattern for the first three principal energy levels is as follows:
1
2
3
1s
2s
2p
3s
3p
3d
Principal
Energy
Levels
Basic set of
sub-energy
levels
Further splitting observed
when the atom is placed in
a magnetic field
1s
3s
five d energy
levels
2p
x
2p
y
2p
z
3p
x
3p
y
3p
z
2s
49
The Fourth (and last!!) Quantum Number
Stern-Gerlach Experiment (1922): a beam of silver (Ag) atoms was
passed through an inhomogeneous (constantly varying) magnetic field
N
S
Ag
atoms
inhomogeneous
magnetic field
50%
50%
Ag
108
47
atomic mass
atomic number: number
of protons in the atom
Note that the
Ag atoms have
an odd number
of electrons
50
We need a fourth quantum number to deal with this property of the
electron. This is the Spin Quantum Number and has two possible
values: + and - , corresponding to the direction of spin. Once again
these numbers are effectively just labels.
Explanation of the Stern-Gerlach Effect
It is suggested that the electrons can spin on their axis and so generate
two possible magnetic fields which are oppositely orientated.
The odd electron in a silver atom determines its overall magnetic character
and results in 50% having one orientation and 50% the other.
In the varying magnetic field, one type of atom is deflected one way while the
other type goes in the opposite direction
51
Information from Quantum Numbers
The quantum numbers allow us to identify a particular electron in an atom
The first three provide us with information about the energy level (orbital)
occupied by the electron
Principal Quantum
Number (1, 2, 3, etc.):
size of orbital
Secondary Quantum
Number (s, p, d, f, etc.):
shape of orbital
Magnetic Quantum
Number (subscript
x, y,z, etc.):
orientation of orbital
The Fourth Quantum Number tells us about the direction of spin of the
electron but nothing about the energy level/orbital
3p
x
52
1s
2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f 5g
6s 6p 6d 6f 6g
The complete list of accommodation options (energy levels) for an electron in an
atom is mapped out in the following diagram:
2p: a set of three energy
levels, 2p
x
, 2p
y
and 2p
z
.
3d: a set of 5 energy levels
The superimposed arrows give the ordering of the energy levels in terms
of energy. Start at the tail of the arrow in the top left-hand corner and read
along it to its head. Then continue on to the tail of the next arrow down.
Complete list of energy levels for an electron in an atom
This gives us the following order:
1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p, etc
Or writing out the family of p orbitals in full:
1s 2s 2p
x
2p
y
2p
z
3s 3p
x
3p
y
3p
z
4s 3d, etc.
53
How are the electrons arranged in an atom?
Why do we want to know?
Chemical properties of a material = f (arrangement of the electrons in
the atoms of the material)
Arrangement of electrons in an atom the electronic
configuration of that atom
Electrons occupy energy levels/orbitals in an atom but which one?
Basic Problem
How do the electrons fit into the orbitals/energy levels? Its like fitting
guests into the rooms of an hotel
54
Rules for filling energy levels with electrons
Rule 1: Aufbau Principle - fill the lowest available energy level first
Start with the simplest atom hydrogen. This has an atomic number
(AN) of 1 (one electron / one proton). It is written as H
1
Hydrogen (H
1
): 1s
1
(one electron in the 1s energy level)
Helium (He
2
): 1s
1
2s
1
? 1s
2
? Can we put more than one
electron in the 1s level?
building-up
55
Number of protons (=
number of electrons
for a neutral atom)
=> Helium (He
2
): 1s
2
Lithium (Li
3
): 1s
2
2s
1
Beryllium (Be
4
): 1s
2
2s
2
Boron (B
5
): 1s
2
2s
2
2p
x
1
Because 2p
x
2p
y
in terms of
energy, the Aufbau Principle
doesnt distinguish between
these two possibilities. We need
another rule!
These two rules allow us to deal with the next few atoms:
Rule 2: Pauli Exclusion Principle - each individual energy level can hold
two electrons
1s: two electrons
2p: six electrons (2p
x
2
2p
y
2
2p
z
2
)
4d: ten electrons (each d energy level is a set of five energy levels)
But:
Carbon (C
6
): 1s
2
2s
2
2p
x
2
?
1s
2
2s
2
2p
x
1
2p
y
1
?
56
Wolfgang Pauli
1900 - 1958
Carbon (C, AN = 6): 1s
2
2s
2
2p
x
2
Incorrect by Hunds Rule
1s
2
2s
2
2p
x
1
2p
y
1
Correct by Hunds Rule
We can use these three rules to write down the
electronic configuration of all the other atoms
Nitrogen (N
7
): 1s
2
2s
2
2p
x
1
2p
y
1
2p
z
1
Oxygen (O
8
): 1s
2
2s
2
2p
x
2
2p
y
1
2p
z
1
Fluorine (F
9
): 1s
2
2s
2
2p
x
2
2p
y
2
2p
z
1
Neon (Ne
10
): 1s
2
2s
2
2p
x
2
2p
y
2
2p
z
2
Rule 3: Hunds Rule of Maximum Multiplicity (Public Bus Rule) -
each energy level of the same energy (known as degenerate energy
levels) are filled singly before pairing occurs
57
Friedrich Hund
1896-1997
Problem: write out the electronic configurations of the following atoms:
Calcium (Ca
20
)
Selenium (Se
34
)
Xenon (Xe
54
)
We can write out the electronic configuration in detail:
Copper (Cu
29
): 1s
2
2s
2
2p
x
2
2p
y
2
2p
z
2
3s
2
3p
x
2
3p
y
2
3p
z
2
4s
2
3d
9
Or we can combine the p orbitals:
Cu
29
: 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
9
The best thing is to write it out in detail. You are not expected to know the
labels for the individual d orbitals - so for copper its just 3d
9
58
Lithium (Li
3
): 1s
2
2s
1
Sodium (Na
11
): 1s
2
2s
2
2p
6
3s
1
Potassium (K
19
): 1s
2
2s
2
2p
6
3s
2
3p
6
4s
1
Rubidium (Rb
37
): [Ar] 4s
2
3d
10
4p
6
5s
1
Cesium (Cs
55
): [Ar] 4s
2
3d
10
4p
6
5s
2
4d
10
5p
6
6s
1
[Ar]: shorthand for the set of energy levels and electrons in the argon atom
Writing down the electronic configurations of atoms allows us to see
relationships between them
The properties of an atom chemical and physical - are determined by its
electronic configuration
The most important electrons are those in the outermost energy level (orbital)
Each atom in this list has the same number (1) and type of electron (s)
in the outermost energy level (orbital)
Atoms with similar electronic structures, and thus similar properties, occur at
intervals as we build up to larger atoms. This is the concept of periodicity
but it was discovered before anything was known of orbitals/energy levels
59
Periodicity and the Periodic Table
1869 Mendeleev (a Russian) and Meyer (a
German) discovered that if atoms were listed in
order of increasing atomic mass, the list could
be cut up into sections which when placed
under each other gave columns of
atoms/elements with similar chemical properties
H He Li Be B C N O F Ne Na Mg Al Si P S Cl Ar K Ca
Na Mg Al Si P S Cl Ar
K Ca
etc.
etc.
Atoms with similar
properties
Columns of atoms with
similar properties
Increasing
atomic mass
Dimitri Ivanovitch
Mendeleev 1834-1907
60
61
Working with the Periodic Table
s
p
d
f
* Type of outermost electron (energy level)
1. The Periodic Table (PT) consists of a number of blocks in each of which
the atoms have the same type of electrons in their outermost energy
level/orbital
62
4. Mendeleev used the PT to predict the existence and properties of
elements which were unknown at the time:
B C N O F
Al Si P S Cl
Zn As Se Br
Mendeleev realised that this section of the
PT was incorrect as elements with totally
different properties appeared in the same
column, eg N, P, Br. Br in fact is like F and
Cl, Se like O and S and As like N and P.
X, predicted by
Mendeleev in 1871
and given the name
ekaaluminium.
Discovered in1875.
and called gallium.
Y, predicted by
Mendeleev in 1871 and
given the name
ekasilicon. Discovered
in 1876 and called
germanium
B C N O F
Al Si P S Cl
Zn X Y As Se Br
2. All the elements in a particular column have similar chemical
properties
3. Instead of studying ~110 elements we have to study a much smaller
number of element families (columns)
Two new elements
63
Atomic Properties and the Periodic Table
B C
Al Si
As
P
Ge
Sb
Se
Po At Rn Bi Pb
Te I
Sn
Fe
Na
Increasing
Metallic Character
The zig-zag line marks the boundary between metals and non-metals
Non-metals
Metals
1. Metallic Character (eg conductivity)
The boundary is not sharp: there is a gradual increase in metallic
character from right to left sodium (Na) is more metallic than iron (Fe)
An element along the boundary can behave as both a metal (conductor)
and a non-metal (insulators)
Silicon (Si) and germanium (Ge) are semiconductors
Phosphorus (P) and arsenic (As) are used as semiconductor
dopants
64
2. Atomic Size
Li
1.52
Be
1.11
B
0.88
C
0.77
N
0.70
O
0.66
F
0.64
Na
1.86
K
2.31
Rb
2.44
Cs
2.62
(angstrom): 1 = 10
-10
m
Decrease in
atomic size across
row/period
Increase in
atomic size
down a
column/group
65
But when you add an electron you also add a proton and so the
nuclear charge is increasing. No change in PQN and increase in
nuclear charge means => electron/nucleus force increases and the
size of the atom decreases
Down a column/group
There are two effects which lead to an increase in the atomic size:
1. As we go down each atom has an electron in an orbital with a
larger PQN => the atomic size increases
Li: 1s
2
2s
1
Na: 1s
2
2s
2
2p
6
3s
1
Across row/period
No change in the PQN of the outermost electron and so in
principle there is no change in the size of the atom
Li: 1s
2
2s
1
Ne: 1s
2
2s
2
2p
6
2. As we go down the outermost electron is progressively further from
the nucleus and so is increasingly shielded or screened from it by
the electrons in the orbitals between it and the nucleus => atomic
size increases
66
3. Ionization Energy (IE) (Ionization Potential)
This is the energy required to remove the most loosely bound (outermost)
electron from a gaseous atom
-