CH120 Chemistry: molecular science

CH130 Chemistry: world of the molecule

Lecturer: Dr. Niall Geraghty, Chemistry Department,
Ext. 2474; email: niall.geraghty@nuigalway.ie
CH120: Medicine (0MB), Biomedical Science (1BO)
CH130: Physics with Medical Physics (1BPM), Mathematical Science
(1BMS), Biotechnology (1BY), Earth and Ocean Sciences (1EH),
Environmental Science (1EV), Physics and Applied Physics (1BPP)
Lectures: 72 (2 Semesters)
School of Chemistry, National University of
Ireland, Galway
1
Practicals
Essential for Practicals: Protective glasses and white laboratory coat
(SU shop)
Semester 1 and 2
Physics with Medical Physics (1BPM), Mathematical Science (1BMS),
Biotechnology (1BY), Earth and Ocean Sciences (1EH), Environmental
Science (1EV), Physics and Applied Physics (1BPP): Semester 1 and 2
Examination: MC/Short Answer; details to be announced
Semester 2
Biomedical Science (1BO), Medicine (0MB)
Examination: MC/Short Answer; in-lab examination
2
Practical timetable for CH130 Chemistry: the world of the
molecule 2012-2013 Semester 1 and Semester 2
Day Group Pre-laboratory Lecture
Class
Supervisor
Monday 1EV, 1BPM
Tyndall Lecture Theatre, 3.00 pm,
Microbiology Department
Dr. Leigh
Jones
Wednesday
1BY, 1EH,
1BMS
Darcy Thompson Lecture Theatre
3.00 pm, Concourse
Dr. Judith
Wurmel
Thursday 1BPP
Tyndall Lecture Theatre, 3.00 pm,
Microbiology Department
Dr. Judith
Wurmel
3
Registration for Practicals
Venue: First Year Laboratory, School of Chemistry (Concourse level,
first right on corridor to the right of the Dillon Theatre, about 30 m from
the Concourse)
Registration fee (includes laboratory manual and molecular
models): 20.00
Time/date: Thursday, September 20
th
, 2.30-4.30
4
Day Group Pre-laboratory Lecture
Class
Supervisor
Monday 1BO
3.00pm Room 223, School of
Chemistry.
Dr. Leigh Jones
Thursday 0MB 3.00pm Tyndall Theatre Dr. Judith Wurmel
Practical timetable for CH120 Chemistry: molecular science
2012-2013 Semester 2
Registration for Practicals
Venue: First Year Laboratory, School of Chemistry (Concourse level, first
right on corridor to the right of the Dillon Theatre, about 30 m from the
Concourse)
Registration fee (including laboratory manual): 10.00
Time/date: 1BO: Monday, January 7
th
, 2.00pm
0MB: Thursday, January 10
th
, 2.00pm
Textbook
The most important textbook is your lecture notes.
If you have never done Chemistry and are having problems: first try
using a Leaving Certificate or A-level textbook
Recommended university texts: (1) Chemistry: Human Activity,
Chemical Reactivity, P. Mahaffy, Nelson Thomson Learning. (2)
Chemistry: the Central Science, Brown, LeMay, Bursten and
Murphy, 11ed., 2009, Pearson Education
Tutorials
One tutorial/week
1BY, 1EV, 1EH, 1BMS, 1BPP, Monday, 2.00-3.00, Larmor Theatre;
1BO, 0MB, 1BPM: Wednesday, 5.00-6.00, Dillon Theatre (Semester 1
and 2)
5
CH120 Chemistry: molecular science
Medicine (0MB)/Biomedical Science(1BO):
Written examinations: Semester 1, 32.5%; Semester 2, 32.5% Clicker
based assessment: 5%
Practical: 20% Continual Assessment; 10% Short Answer/MCQ
Examination (in-lab)
Examinations
6
CH130 Chemistry: the world of the molecule
Physics with Medical Physics (1BPM), Mathematical Science
(1BMS), Biotechnology (1BY), Earth and Ocean Sciences (1EH),
Environmental Science (1EV), Physics and Applied Physics (1BPP)
Written examinations: Semester 1, 32.5%; Semester 2, 32.5% Clicker
based assessment: 5%
Practical: 20% Continual Assessment; 10% Short Answer/MCQ
Examination (details to be announced)
CHEMICAL
ARITHMETIC
PHYSICAL
CHEMISTRY
THERMODYNAMICS
STRUCTURE
OF THE ATOM
PROPERTIES
ATOMS
ATOMS
COMBINING TO
GIVE MOLECULES
MOLECULES
GASES
LIQUIDS
SOLIDS
KINETICS
ORGANIC
CHEMISTRY
INORGANIC
CHEMISTRY
INDUSTRIAL PROCESSES
ENVIRONMENTAL CHEMISTRY
MEDICAL APPLICATIONS
Course Map
7
The Year 1900
Information about the structure of an atom: a set of
jigsaw pieces waiting 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(o) particles
8
Matter is made up of indivisible particles: atoms
Jigsaw Piece 1:
John Daltons Contribution 1803
All atoms of an element have the same properties eg mass
Chemical reactions / chemical changes: atoms changing the way
they are combined to one another
- atoms combining to give molecules
- atoms in one molecule interacting with atoms in another
molecule
Atoms combine in fixed ratios of whole numbers: this idea led to
the concept of atomic mass (atomic weight), the first measurable
property of an atom






1766-1844
9
Earth
45 km
35 km
Stratosphere
Ozone
Layer
sun's radiation,
including
UV-A and UV-B
An example of how chemical change involves atoms and
molecules the formation and role of the Ozone Layer
Ultraviolet (UV) light
A form of electromagnetic radiation characterised by its frequency ()
and wavelength ().
We can also consider it to consist of little packets of energy called photons.
There are two forms of UV light: UV-A (near UV, low energy, long , low v)
and UV-B (far UV, high energy, short , high v).
10
Effect of UV-B
Energy from UV-B light
breaks the bond
Overall UV-B
is absorbed
and Ozone
Layer created
+
UV-B
photon
oxygen
molecule (O
2
)
oxygen
atoms (2) (2O)
bond between
atoms
We write
this as
O
2
2O
UV-B
This reaction is
followed by
O
2
+ O
ozone
molecule
O
3
11
Effect of UV-A
The Ozone Layer
absorbs UV-A photons.
The ozone molecules
are destroyed but are
regenerated
Overall both UV-A and UV-B photons are removed from the sunlight
continuing on towards the Earths surface where they could damage both
plants and animals
O
3
UV-A
UV-A
O + O
2
O
2
+ O O
3
The chemical reactions in the Ozone Layer involve three forms of oxygen:
oxygen atoms (O), oxygen molecules (O
2
) and ozone molecules (O
3
)
12
Chlorofluorocarbons (CFCs or Freons) and the Ozone Layer
Example: CF
2
Cl
2
(dichlorodifluoromethane)
C F
Cl
F
Cl
Properties: gases, non-toxic, inert, non-corrosive, easy and cheap to make
13
History and Use
1930 Developed due to need to find alternative to refrigerants such as
ammonia (NH
3
)
1991 682 x 10
6
kg used worldwide: refrigerants (32%), blowing agents
(28%), dry cleaning agents (20%), aerosol propellants (18%)
1973 Catalytic role of chlorine in ozone decomposition discovered
1985 Polar ozone depletion discovered over Antartica and linked to CFCs
1987 Montreal Protocol under which producton and use of CFCs was to be
phased out by the end of 1995 in developed countries
http://www.theozonehole.com
http://ozonewatch.gsfc.nasa.gov
14
So whats the connection between the ozone layer and CFCs?
Cl + O
3
ClO + O
2
ClO + O O
2
+ Cl
CF
2
Cl
2
photon of
UV light
CF
2
Cl + Cl
chlorine
atom
CFC molecules are stable and so remain in the atmosphere for many
years, slowly drifting up to the edge of the stratosphere where they come
into contact with photons of UV light and the ozone layer
Chlorine atoms are thus the real problem as one Cl atom can destroy
many O
3
molecules. This gives rise to holes in the ozone layer through
which UV-A can pass
15
The Present and the Future
Although the use of CFCs is effectively banned as a result of the
Montreal Protocol, there will be an effect on the ozone layer for many
years due to the CFCs already in the atmosphere
Size of Antarctic Ozone Hole by NASA satellite monitoring:
September 2000 29.5 x 10
6
km
2

September 2006 29.4 x 10
6
km
2

16
Hole in the
Ozone Layer
over
Antarctica,
September
14
th
2009
Blue: low levels
of ozone
17
Atomic Mass (Weight) Concept

Example 1
Known: A 1 g hydrogen + excess oxygen 9 g water
1 g hydrogen combines with 8 g oxygen
Example 2
Known: A 1 g magnesium + excess oxygen 1.67 g magnesium oxide
1g magnesium combines with 0.67 g oxygen
B Formula of water: H
2
O
A and B by weight: 1 atom O 16 atoms H
B Formula of magnesium oxide: MgO
Then as: 1 atom O 16 atoms H
And : 1.5 atoms O 1 atom Mg
by weight 1 atom Mg 24 atoms H
A and B by weight: 1 atom Mg 1.5 atoms O
18
the first measurable
property of an atom
In the same way we could compare the mass of any atom
with that of hydrogen. In practice we use a carbon atom,
rather than a hydrogen atom, as the standard
Atomic Mass (Weight): the mass (weight) of an atom of an
element relative to the mass of the carbon atom taken as 12
19
Jigsaw Piece 2: Fundamental Particles 1874 -1930
(A) The electron
1874 Suggested as a good idea by Stoney as the basic unit of negative
charge
1897 Using a cathode ray tube (CRT) Thomson showed it actually
existed
Basic CRT: as the voltage was increased, light was produced in the tube
and patterns of bright and dark spaces are observed. These were
explained by assuming there were rays (cathode rays, CRs) moving
away from the cathode
glass tube
metal
electrodes
10,000 - 20,000V
low pressure
inside tube
~ 1/10,000atm
anode
cathode
cathode
rays
+ -
20
A slightly modified CRT can be used to study the properties of CRs
The direction of deflection indicates that the particles in the rays are
negatively charged
+
u
+
_
_
o e/m (charge/mass) of the CR particles; e/m = 1.76 x 10
11
C/kg. Other
experiments show that the charge on each particle is 1.6 x 10
-19
C and so
their mass is 9.1 x 10
-31
kg
The properties of these CRTs f(gas in tube, cathode metal). Thus they
are fundamental particles. Today we use the term electrons for these
CR particles.
21
J.J. Thomson, The London, Edinburgh, and
Dublin Philosophical Magazine and Journal of
Science, October 1897. p. 296
Diagram from Thompsons original publication
1856 -1940
22
+
-
Positive Rays
Cathode Rays
CRT
(B) The proton
Again discovered using a CRT
Positively charged particles (Positive Rays) were observed behind a
cathode (-) with holes cut in it
The particle from hydrogen had a charge equal to that of the electron but
its mass was 2000 times greater
Particles from other gases had e and m values which were multiples of
the hydrogen values
The particle formed by hydrogen called a proton was considered to
be the basic unit of positve charge and a fundamental particle
e/m = f(gas in CRT)
hydrogen gas gave
the particle of
smallest mass
23
(C) The neutron
This is a neutral particle with the same mass as the proton
Suggested by Rutherford in 1920 but only shown to exist by Chadwick
in 1932
(D) Other sub-atomic particles
Neutrinos, mesons, positrons, etc.
These are not important in terms of the behaviour of molecules
There are even sub-proton/electron/neutron particles called quarks
24
Particle Relative Mass Relative Charge
Electron 0 -1
Proton 1 +1
Neutron 1 0
A Comparison of Sub-atomic Particles
25
Jigsaw Piece 3: The Phenomenon of Spectra
1663 Newton discovered that white light, for example from
the sun, could be broken up into light of different
colours (different frequencies / wavelengths) by
passing it through a glass prism. The spread of
different colour light is known as a spectrum
infrared
light
ultraviolet
light
beam of light produced by passing
sunlight through a slit
26
Isaac Newton in
1689, aged 46
1814 The German astronomer, Fraunhofer, using a diffraction grating
(effectively a super prism) showed that the suns spectrum
contained a number of dark lines, almost as though light of a very
precise colour (wavelength/frequency) had been removed.
1800 Infrared light was discovered by Herschel as a result of its heating
effect on a thermometer placed beyond the red end of the suns
spectrum
1801 Ultraviolet light was discovered by Ritter as a result of its darkening
effect on light sensitive crystals placed beyond the violet end of a
spectrum
red light section of
suns spectrum
27
wavelength (, lamda) increasing
frequency (v, nu
)
decreasing
-rays X-rays
UV VIS IR Microwaves Radiowaves
V R
*

source
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
-

Gaseous atom: isolated

from other atoms and
so IE is not affected by
atoms environment
Most loosely
bound electron
A(g) A(g)
+
+ e
-
67
Down Group: The size of the atom increases (see above) => the outermost
electron is held further from the nucleus and so IE decreases
Li
519
Be
900
B
799
C
1088
N
1402
O
1314
F
1682
Ne
2079
Na
494
K
418
Rb
403
Cs
375
kJ mol
-1

Increase in IE
across
row/period
Decrease in IE
down a
column/group
General
Trends
IE values and the Periodic Table
General Trends
Across Row: The size of the atom decreases (see above) => the outermost
electron is held closer to the nucleus and so IE increases
68
The beryllium (Be)/boron (B) problem: is the IE of Be too high or is that of
B too low?
Outermost electron is in full
energy level: very stable and
so a lot of energy is needed
to remove electron
A full energy level: very stable
and so not a lot of energy is
needed to remove 2p
x
electron to
produce it
Be (AN = 4) Be
+
+ e
-
1s
2
2s
2
1s
2
2s
1
B (AN = 5) B
+
+ e
-
1s
2
2s
2
2p
x
1
1s
2
2s
2
Overall the Be value is higher and the B value is lower than expected
Key Point: a set of full orbitals/energy levels is very stable
69
The N/O problem: this is the same as that for Be and B. The explanation
is also similar: a half full p orbital has a degree of stability associated with it
N
7
: 1s
2
2s
2
2p
3
O
8
: 1s
2
2s
2
2p
4
The effect is much less important than that associated with a full orbital
Problem: write out a detailed explanation for the N/O IE problem as was
done for Be/B above
A(g) A(g)
+
+ e
-
A(g)
+
A(g)
2+
+ e
-
A(g)
2+
A(g)
3+
+ e
-
3
rd
IE
1
st
IE
2
nd
IE
Problem: the First, Second and Third IE, etc. for an element can be defined
as indicated below:
Given the above, account for the following data which relate to beryllium (Be
4
):
1
st
IE, 900; 2
nd
IE, 1750; 3
rd
IE, 14,800 kJ mol
-1

70