CHEMISTRY I

Lecture 2, 3 & 4
Atomic
Structure
What is Chemistry?

• The study of matter and energy and the interactions between

them.
• We begin by learning about
matter and its building blocks-the elements
• Today we know that matter is made up of atoms however
The debate about the composition of matter began as early as 500 B.C. by
Greek Philosophers
Philosophers pursued wisdom, knowledge, and truth through argument and
reason
Proposition by Empedocles (450 B.C)

• Empedocles proposed that matter was composed of four fundamental

‘elements’ in various proportions
 earth
 air,
 fire and
 water in various proportions.

• Thus earth, air, fire & water were considered as the elemental substances
that ultimately made up matter
• However the earliest atomic theory was proposed in 478 B.C. by
Leucippus which was recorded by his student Democritus around 420 B.C.
Leucippus and Democritus Theory

• This theory was derived from thinking on

 What would happen if we continuously keep dividing matter’.

• argued that matter had an ultimate, tiny, indivisible particle.

 They called this particle the atom after the Greek word ‘atomos’ meaning ‘indivisible’.

• Hence atoms were the smallest indivisible part of matter.

• According to Democritus, the different materials of the world were
due to atoms of different shapes, the way they are arranged and
positioned.
• This theory was later rejected by another Greek philosopher,
Aristotle (384-322 B.C).
Aristotle: 384-322 B.C

• Adopted and developed the ideas of Empedocles.

• According to him the four elemental substances that constitute matter
i.e. earth, fire, air and water were associated with four qualities
 hot, moist, cold and dry
 i.e. Earth was dry and cold; water was cold and moist, air was moist and hot and fire was
hot and dry.
• He argued that:
 every substance was composed of the four fundamental elements in various proportions
and
 that one element could be converted into the other by the addition or removal of the
appropriate qualities.
•

Aristotle: 384-322 B.C…….

• At that time there were no experimental evidence:

 therefore the best debater was the person assumed correct.

• During his time, Aristotle was the most influential Greek scientific
philosopher
 the scientists and philosophers of the time accepted his theory.

• With the acceptance of Aristotle’s ideas, the concept of the atom by

Leucippus and Democritus could not be developed any further
Scientific Revolution

• In the late 16th century, the scientific approach to understanding

nature became established

• for the next 150+ years, observations about nature were made that
could not easily be explained by the infinitely divisible matter concept

• John Dalton (1766-1844), an English school master revived the concept

of atom and proposed an atomic theory of matter based on scientific
laws that existed at the time.
Dalton’s Atomic Theory

• Proposed that:
All matter is composed of tiny, indestructible particles called atoms
All atoms of a given element are identical i.e. have the same mass and size
Atoms of different elements have different masses and sizes.
Atoms combine in simple, whole-number ratios to form molecules of
compounds such as one to one, two to one, two to three etc.
Atoms of two elements may combine in different ratios to form more than
one compound.
In a chemical reaction, atoms are neither created nor destroyed but they
simply rearrange the way they are attached to form new substances.
Dalton’s Atomic Theory…..

• Dalton’s atomic theory successfully explained the laws of chemical

combination.

• It acted as a major step towards the development of chemistry.

• Later experiments showed that the atom is not indivisible but has an
internal structure.
Sub atomic parts of the atom

• Scientific investigations in the 19th and 20th centuries showed that an

atom has an internal structure.

• Further investigations led to the discovery of the three subatomic

particles:
 Electrons
 protons and
 neutrons.
Cross-sectional view of an atom
• The atom contains a tiny dense center
called the nucleus
Electrons
• the nucleus has essentially the entire
mass of the atom

• The nucleus is composed of protons

and neutrons

• The nucleus is positively charged

• Electrons are dispersed around the

nucleus
General features of the atom
today.
• The atom is an electrically neutral, spherical entity composed of a positively
charged central nucleus surrounded by one or more negatively charged electrons.

• The atomic nucleus consists of protons and neutrons (the only exception is the simplest
hydrogen which is a single proton).
Discovery of the Electron: J.J. Thomson

• The electron was discovered in 1897 by an English physicist Sir

Joseph J. Thomson (1856-1940) with the use of the cathode ray glass
tube

• Cathode ray glass tube:

contains metal electrodes from which almost all the air has been evacuated
when connected to a high voltage power supply, a glowing area is seen
emanating from the cathode
Cathode Ray Tubes

anode

cathode

15
J.J. Thomson
• believed that the cathode ray he saw in the tube was composed
of tiny particles with an electrical charge

• designed an experiment to demonstrate that there were

particles in cathode rays by attempting to deflect their path.

16
Thomson’s Experiment
Investigate the effect of placing an electric field around tube
(1) charged matter is attracted to an electric field
(2) light’s path is not deflected by an electric field

+++++++++++ anode
catho
de(-) (+)

------------
- -
Power Supply
+

17
Thomson’s Results
• Thomson concluded that cathode rays are made of tiny particles and
the particles:
move at a very high speed
have a negative charge because the beam always deflected toward the + plate
have a mass of about 1/2000 of a hydrogen atom (smallest atom).
• the amount of deflection was related to the charge and mass of the
particles.
• The particles were the same regardless which gas was used in the
container or the metal used as the electrode.

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Thomson’s Results…..
• He believed that the particles were pieces of atoms and
therefore the ultimate building blocks of matter
 these cathode ray particles later became known as electrons
• He believed that an atom is composed of electrons
surrounded by a field of positive charge that balances the
negative charge.
 Thomson’s model is known as the “plum-pudding” model.
• Plum-pudding model:
 Atom is mostly empty.
 Mass is due to electrons.
 There are no positive particles inside.

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Electrons

• Since Thomson’s discovery to date, an electron is defined as

negatively charged particle (a charge of -1.60 x 1019 C)
with mass of 9.107 x 10-28 g (approximately 1/2000 of the mass of a
hydrogen atom).
• This mass is an equivalent of 0.0005486 atomic mass units (amu).
One atomic mass unit (1 amu) is equivalent to 1.660 x 10-24 g.
• electrons are particles found in all atoms
• cathode rays are streams of electrons
•

Discovery of the Proton

Radioactivity
• in the late 1800s, Henri Becquerel and Marie Curie discovered that certain
elements would constantly emit small, energetic particles and rays

• these energetic particles could penetrate matter

• Ernest Rutherford discovered that there were three different kinds of

emissions
alpha,α, particles with a mass 4x H atom and + charge
beta,β, particles with a mass ~1/2000th H atom and – charge
gamma,γ, rays that are energy rays, not particles
Rutherford’s Experiment
• He wanted to verify the plum-pudding model.
• How can you prove something is empty?
• put something through it
• use large target atoms
 use very thin sheets of target so do not absorb “bullet”
• use very small particle as bullet with very high energy
 but not so small that electrons will affect it

• bullet = alpha particles, target atoms = gold foil

• Gold foil is malleable.

23
Rutherford’s Experiment

24
Rutherford’s Results
• Over 98% of the a particles went straight through

• About 2% of the a particles went through but were deflected by

large angles

• About 0.01% of the a particles bounced off the gold foil

“...as if you fired a 15” cannon shell at a piece of tissue paper and it came
back and hit you.”

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Rutherford’s Conclusions
• Atom mostly empty space
because almost all the particles went straight through

• Atom contains a dense particle that was small in volume compared to

the atom but large in mass
because of the few particles that bounced back
He proposed the existence of the nucleus.

• This dense particle was positively charged

because of the large deflections of some of the particles.
This led to discovery of protons.

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Rutherford’s Interpretation – the Nuclear Model

• The atom contains a tiny dense center called the nucleus

the amount of space taken by the nucleus is only about 1/10 trillionth the volume of the
atom

• The nucleus has essentially the entire mass of the atom

the electrons weigh so little they give practically no mass to the atom

• The nucleus is positively charged

the amount of positive charge balances the negative charge of the electrons

• The electrons are dispersed in the empty space of the atom surrounding the nucleus
The Neutron
• Further experiments also revealed that the atomic masses
were more than that expected from the number of protons
and electrons present in an atom.

• A third subatomic particle was discovered by Sir James

Chadwick in 1932.
This particle was found to be of zero charge i.e. bearing neither a
positive nor a negative charge and with a mass similar to that of a
proton (1.675 x 10-24 g). He called this particle a neutron.

29
Atomic Mass Units (amu)
• The masses for atoms and sub-atomic particles are very small,
hence, we cannot express them in grams or kilograms.
• We use a relative scale to describe their masses (compare the small
particles amongst themselves).
• An appropriate unit for reporting them is the atomic mass unit
(amu).
It is based on C-12 (has 6 protons and 6 neutrons).
The atomic mass unit is defined as one-twelfth of the mass of a C-12.
• By convention: 1 atomic mass unit (amu) = 1.66 x 10-24 g

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Atomic Mass Units (amu)….
• Therefore the mass of a proton in atomic mass units can be calculated as
follows:

Massof proton1.67x 10-24 g

1atomicmassunit 1.66x 10-24 g
1.67x 10-24 g
 Massof protonin amu -24
x 1amu1.006amu
1.6610 g

• Using similar calculation, the mass the mass of an electron is 0.00055 amu,
which is generally too small and negligible

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Relative Mass and Charge

• It is sometimes easier to compare things to each other rather than to an outside

standard
• when you do this, the scale of comparison is called a relative scale
• we generally talk about the size of charge on atoms by comparing it to the amount
of charge on an electron, which we call -1 charge units
proton has a charge of +1cu
protons and electrons have equal amounts of charge, but opposite signs
• we generally talk about the mass of atoms by comparing it to 1/12th the mass of a
carbon atom with 6 protons and 6 neutrons, which we call 1 atomic mass unit
 protons have a mass of 1amu
 electrons have a mass of 0.00055 amu, which is generally too small to be relevant

32
•

Fundamental particles of an atom

• Based on discoveries by Thomson, Rutherford and Chadwick, we can

conclude that conclude that atoms are not indivisible but have an internal
structure.

• The internal structure of an atom consists of three fundamental particles, the

electron, proton and the neutron whose characteristics

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Characteristics of the Fundamental Particles of
matter.
Subatomic Mass Mass Location Charge Symbol
Particle g amu in atom
Proton 1.67 1.006 nucleus +1 p, p+, H+
x 10-24
Electron 9.1 0.00055 empty -1 e, e-
x 10-28 space
Neutron 1.67 1.006 nucleus 0 n, n0
x 10-24

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Atomic Number (Z)

• The number of protons is unique to each element and is a

fundamental characteristic of an element.
It is known as the atomic number (symbol Z).
The atomic number specifies the element that any atom belongs to.

• For example:
Hydrogen has an atomic number of 1, therefore has 1 proton
Sodium has an atomic number of 11, therefore has 11 protons

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Mass Number (A)
• The mass of an atom is due to protons and the neutrons that
are present in its nucleus.
 Electrons have negligible mass.

• The sum of protons and neutrons in an atom is known as the

mass number (symbol, A) of the atom.

• For example:
 Carbon-14, another kind of carbon atom has six protons and eight neutrons in its
nucleus. Therefore its mass number is 14 amu.

36
Representing Composition of an Atom
• To represent the composition of any particular atom, you need to specify its
number of electrons, protons and neutrons.
• Use symbolism: A
Z E
• Where, E is the symbol of the element, Z the atomic number and A the mass
number
• each element has a unique name and symbol
symbol has one or two letters
 one capital letter or one capital letter + one lowercase
1 27
H
1 13 Al 4
2 He

37
 Structure of the Nucleus

• Dalton’s atomic theory proposed that all atoms of a given

element have the same mass: Was Wrong!

• Soddy discovered that the same element could have atoms

with different masses, which he called isotopes
there are 2 isotopes of chlorine found in nature, one that has a mass
of about 35 amu and another that weighs about 37 amu
Element Neon has three isotopes with masses of 20, 21 and 22 amu

38
Isotopes
• Atoms with identical atomic number but different atomic mass
number i.e. they have the same number of protons but different
numbers of neutrons
• Isotopes of an element are identified by their mass numbers
protons + neutrons
• Isotopes are sometimes written by putting the mass number
after the name of the element:
Chlorine-35 (Cl-35) and Chlorine-37 (Cl-37)
Neon-20 (Ne-20), Neon-21 (Ne-21) and Neon-22 (Ne-22)
• All isotopes of an element are chemically identical
undergo the exact same chemical reactions

39
Average atomic Mass
• Not all atoms of an element have the same mass
isotopes
• We generally use the average mass of all an element’s atoms
found in a sample in calculations
however the average must take into account the abundance of each
isotope in the sample
• We call the average mass the atomic mass
A to m ic M a s s   fr a c tio n a l a b u n d a n c e o f is o to p e n  m a s s o f is o to p e n

40
Average Atomic masses
• The observed atomic mass of an element is a weighted average
of the weights of all the naturally occurring atoms
the percentage of an element that is 1 isotope is called the isotope’s
natural abundance
• For example: the atomic mass of chlorine is 35.5 amu. Why?
Cl has two isotopes Cl-35 and Cl-37 with natural abundance of 75 and
25% respectively

 75   25 
AvgeAtomicmass 35x    37x  amu35.50amu
 100  100

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Average Atomic masses
• Neon has three isotopes: Ne-20, Ne-21 and Ne-22 with natural
abundances of 90.48, 0.27 and 9.25%, respectively

• Its average atomic mass:

 90.48  0.27  9.25

AvgeNe mass 20x    21x    22x  amu
 100   100   100 
 20.19amu

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Mass Spectrometry

• Masses and abundances of isotopes are measured with a mass

spectrometer
• atoms or molecules are ionized, then accelerated down a tube
some molecules into fragments are broken during the ionization process
these fragments can be used to help determine the structure of the
molecule
• their path is bent by a magnetic field, separating them by mass
• similar to Thomson’s Cathode Ray Experiment
Mass Spectrometer
Mass Spectrum

• mass spectrum is a graph that gives

the relative mass and relative
abundance of each particle
• relative mass of the particle is
plotted in the x-axis
• relative abundance of the particle
is plotted in the y-axis
Example: If copper is 69.17% Cu-63 with a mass of 62.9396 amu and the rest Cu-65 with a mass of 64.9278 amu, find copper’s atomic mass
Practice Questions

1. Carbon consists of two isotopes that are stable (C-12 and C-13). Assuming that
98.89% of all carbon in a sample are C-12 atoms, what is the atomic mass of carbon?

2. The chlorine present in PVC has two stable isotopes:35Cl, with a mass of 34.97amu
and 75.77% abundance; and 37Cl,with a mass of 36.95amu.What is the atomic mass
of chlorine?
Applications of isotopes
• Elephants are hunted for the ivory in their tusks. Game wardens use
isotopes to track where elephants are going so they can help protect
them.

• If an elephant eats plants from a wet climate, the ratio of N-15 to N-14
in the hair will be lower than is typically found in nature. If they graze
plants grown in a dry climate, they will have a higher ratio of N-15 to N-
14 than normal.
Applications of isotopes…
Where would you look for an elephant that had a hair sample with a ratio of
0.0045 N-15/N-14 where the normal ratio is 0.0034 N-15/N-14?
Summary of the Timeline of Atomic Models
Periodic Table & Electron Configurations

51
The Periodic Table

• A chart in which all known elements in the universe having

similar chemical and physical properties are grouped
together.

• The elements are arranged in order of increasing atomic

number

• A very important tool in the study of chemistry!

The periodic Table of the elements: Mendeleev
• Order elements by atomic mass

• Saw a repeating pattern of properties

• Put elements with similar properties in same column

• Used the patterns to predict properties of undiscovered

elements

• Where atomic mass order did not fit other properties,

he re-ordered by other properties

53
Periodic Pattern
Periodic Law – When the elements are arranged in order of
increasing atomic mass, certain sets of properties
recur periodically

54
Elements and the Periodic Table

• element: substance that is made up of one type of atom

• Elements with similar chemical and physical properties are in the

same column

• Exploring Periodic Table:

 Groups or Families: vertical columns (same number of valence electrons)
 designated by a number and letter at top
 Periods: horizontal rows(same number of orbitals)
 Each period shows the pattern of properties repeated in the next period
The Modern Periodic Table

• Main Group = Representative Elements = “A” groups

• Transition Elements = “B” groups

• all metals

• Bottom Rows = Inner Transition Elements = Rare Earth Elements

• metals

• There are 18 groups and 7 periods on the Periodic Table.

56
Presentation of Modern Periodic Table

• The elements are arranged according to the atomic numbers above their
symbols.

• With the exception of hydrogen (H), nonmetals appear at the far right of the
table.

• The two rows of metals beneath the main body of the table are conventionally
set apart to keep the table from being too wide.

• Actually, cerium (Ce) should follow lanthanum (La), and thorium (Th) should
come right after actinium (Ac).
Major divisions of the Periodic Table

58
59
The Quantum-Mechanical Model of
the Atom
 The Nature of Light; Electromagnetic
Spectrum

• The electromagnetic spectrum

includes many different types
of radiation.
• Visible light accounts for only a
small part of the spectrum.
• Other familiar forms include: radio
waves, microwaves, X rays.
• All forms of light travel in waves.
 Wave Characteristics
• Wavelength:  (lambda) distance
between identical points on successive
waves…peaks or troughs.

• Frequency: (nu) number of waves

that pass a particular point in one second.

• Amplitude: the vertical distance

from the midline of waves to the
top of the peak or the bottom of the trough.
 Wave Characteristics
• Wave properties are mathematically related as: c = 
where;
c = 2.99792458 x 108 m/s (speed of light)

l = wavelength (in meters, m)

 = frequency (reciprocal seconds, s 1)

Wave Calculation

The wavelength of a laser pointer is reported to be 663 nm. What

is the frequency of this light?


c 
Wave Calculation Practice
Calculate the wavelength, in nm, of light with a frequency of
3.52 x 1014 s-1.
Wave Interference
• the interaction between
waves is called interference

• when waves interact so that

they add to make a larger wave it
is called constructive interference
waves are in-phase

• when waves interact so they cancel

each other it is called destructive
interference
waves are out-of-phase
Diffraction of waves
• when traveling waves encounter
an obstacle or opening in a barrier
that is about the same size as the
wavelength, they bend around it – diffraction
 traveling particles do not diffract

• the diffraction of light through

two slits separated by a distance
comparable to the wavelength
results in an interference pattern of
the diffracted waves

• an interference pattern is a
characteristic of all light waves
2-Slit Interference of waves
Wave-particle nature of light
• It was observed that many metals emit electrons when a light
shines on their surface
This is called the Photoelectric Effect
Wave-particle nature of light

• Classic wave theory attributed the photoelectric effect to the

light energy being transferred to the electron.

• According to this theory, if the wavelength of light is made

shorter, or the light waves intensity made brighter, more
electrons should be ejected
if a dim light was used there would be a lag time before electrons
were emitted
 to give the electrons time to absorb enough energy
The Photoelectric Effect problem
• In experiments with the photoelectric effect, it was observed that
there was a maximum wavelength for electrons to be emitted.
called the threshold frequency
regardless of the intensity

• It was also observed that high frequency light with a dim source
caused electron emission without any lag time
Photoelectric effect explained
• Einstein proposed that the light energy was delivered to the atoms
in packets, called quanta or photons.
 Based on Planck’s theory.
 Said light has the characteristics of waves and particles.

• the energy of a photon of light was directly proportional to its

frequency
inversely proportional to it wavelength
the proportionality constant is called Planck’s Constant, (h)
and has the value 6.626 x 10-34 J∙s
hc
E h 

Example
Calculate the energy (in joules) of a photon with a wavelength
of 700.0 nm
Exercise

• Calculate the wavelength (in nm) of light with energy 7.85 x 1019 J per
photon. In what region of the electromagnetic radiation does this
light fall?
Atomic Line Spectra
• Planck’s theory along with Einstein’s ideas not only
explained the photoelectric effect, but also made it
possible for scientists to unravel the idea of atomic line
spectra.
Atomic Line Spectra
• When atoms or molecules absorb energy, that energy is often released
as light energy
fireworks, neon lights, etc.

• When that light is passed through a prism, a pattern is seen that is

unique to that type of atom or molecule – the pattern is called an
emission spectrum
non-continuous
can be used to identify the material
 flame tests
Atomic Line Spectra
Examples of Line Spectra

Oxygen spectrum

Neon spectrum
Line Spectra of Hydrogen
• Balmer (initially) and Rydberg (later) developed an
equation to calculate all spectral lines in hydrogen

• The Rydberg equation:

1  
 
 1  1 
R 2
 n1 n2 
2

• R is the Rydberg constant (2.18 x 10 -18J).

Electron Behavior
• The quantum-mechanical model explains the manner electrons exist and behave in
atoms

• Helps us understand and predict the properties of atoms that are directly related to
the behavior of the electrons
 why some elements are metals while others are nonmetals

 why some elements gain 1 electron when forming an anion, while others gain 2

 why some elements are very reactive while others are practically inert

 and other Periodic patterns we see in the properties of the elements

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Bohr’s model of the atom
1. Niels Bohr proposed that
electrons can only have specific
(quantized) energy values
2. radiation is emitted as e- moves
from one energy level to a
lower energy level

1
En = -RH ( )
n2
n (principal quantum number) = 1,2,3,…
RH (Rydberg constant) = 2.18 x 10-18J
Bohr’s Model
• The electrons traveled in orbits that were a fixed distance from
the nucleus- stationary states
 therefore the energy of the electron was proportional to the distance the orbital
was from the nucleus

• Each spectral line corresponds to a specific transition.

• Electrons moving from ground state to higher states require
energy; an electron falling from a higher to a lower state
releases energy.
 Ground state: the lowest energy state of an atom
 Excited state: each energy state in which n > 1

83
Bohr Model of Hydrogen Atom

Excited
states

Ground state

84
A mechanical analogy to the
emission processes. The ball
can rest on any step but not
in between steps.

85
Energy levels

• But, what are the energy levels?

• For each n, there is an energy level designated En.

• The "ground state" of an atom is its lowest energy level, when n = 1.

• We can call that energy level E1.

• Then E2 will be the energy when n = 2, and so on.

Emission process in a hydrogen atom
• Suppose the electron is initially in an excited state, ni.

• Upon emission, electron drops to a lower energy state, nf (subscripts i and f

denote initial and final states, respectively).
• Energy difference between initial and final states is;
ΔE = Ef – Ei

Where

Therefore;

90
Bohr Model of H Atoms
Energy Transitions
• Bohr’s equation can be used to calculate the energy of these
transitions within the H atom.
Example:
• Calculate the energy needed for an electron to move from n =
1 to n = 4.

E  2.041018 J
Note: Its final  initial levels in the calculation.
Example 2: Emission process
• How much energy does a photon emit during a transition from ni = 5 state
to nf = 2 state in the hydrogen atom?
Strategy;
• We are given the initial and final states in the process.
• We can calculate the energy of the emitted photon using Eqn;

Answer = – 4.58 x 10–19 J

Negative sign means emission process

92
• Each horizontal line
represents an allowed
energy level for the
electron in a hydrogen
atom.

• The energy levels are

labeled with their principal
quantum numbers.
Wave character of particles
• Bohr could not explain why electrons were restricted to fixed
distances around the nucleus.

• The Bohr model could also not explain line spectra of atoms
larger than hydrogen.

• Louis de Broglie (1924) reasoned that if energy (light) can behave

as a particle (photon) then perhaps particles (electrons) could
exhibit wave characteristics.
Wave Behavior of Electrons
• De Broglie proposed that particles could have wave-like character have a
wavelength associated with its momentum and mass.
• Recall,

h is Planck’s constant,
m is the mass of the particle, and
v is the velocity of the particle.
Wave Behavior of Electrons
• Particle and wave properties are related by the expression;
λ = where; λ, m, and u are wavelength, mass, and velocity of a
moving particle, respectively.

• Recall; c = λѵ , so u = λѵ (particle doesn’t travel at speed of light)

• Particles of light (photons) h = Planck’s constant (6.63 x 10 – 34 J.s)

posses energy; c = speed of light (3.00 x 108 m/s)
λ = wavelength in nanometers (nm)
E = hѵ = h
ѵ = frequency in s–1 or Hz; 1 Hz = 1 s–1

97
Schrödinger's Wave Equation
Hψ = Eψ
Where H is the Hamiltonian operator, E is the energy, and ψ (psi) is the wave
function.

• An atomic orbital (from Bohr’s model) can be thought of as the wave function of
an electron in an atom.
• An atomic orbital, therefore, has a characteristic energy, as well as a characteristic
distribution of electron density.
• The energy states and wave functions are characterized by a set of quantum
numbers
Quantum Numbers

• There are four different quantum

numbers: n, l, ml, ms needed to
specify the state or probable
location of an electron in an atom

100
Principal Quantum Number, n
Characterizes the energy of the electron in a
particular orbital
– corresponds to Bohr’s energy level

n can be any integer ≥ 1

Shows period (row) in Periodic Table.

 The larger the value of n, the larger the orbital & the farthest
from nucleus the electron is found
 1s o 2s 
 As n gets larger, the amount of energy between orbitals gets
smaller

101
The Shapes of Atomic Orbitals
• The l quantum number (angular momentum) primarily determines the shape of
the orbital
• l can have integer values from 0 to (n – 1)
• Each value of l is called by a particular letter that designates the shape of the orbital
s orbitals are spherical
p orbitals are like two balloons tied at the knots (lobe-shaped)
d orbitals are mainly like 4 balloons tied at the knot
f orbitals are mainly like 8 balloons tied at the knot

102
 Angular momentum (Azimuthal)
quantum number,
for a given value of n, l = 0, 1, 2, 3, … n-1 l

Sublevel
n = 1, l = 0 l = 0 s orbital
First
n = 2, l = 0 or 1 l = 1 p orbital
Second
n = 3, l = 0, 1, or 2 l = 2 d orbital
Third
n = 4, l = 0, 1, 2 or 3 l = 3 f orbital
Fourth
n = 5, l = 0, 1, 2, 3 or 4 l = 4 g orbital
Fifth
n = 6, l = 0, 1, 2, 3, 4 or 5 l = 5 h orbital
Sixth
Defines the shape of the ‘volume’ of space that the electron
occupies

103
The magnetic quantum number, ml
for a given value of l,
there are (2l + 1) integral values
ml = -l, …., 0, …. +l
If l = 0 (s orbital), ml = 0
If l = 1 (p orbital), ml = -1, 0, or 1
if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2

 Describes the orientation of an orbital in space

 The number of ml values indicates the number of
orbitals in a subshell with a particular l value.
104
l = 0, s orbital
Each principal energy state has 1 s orbital
Lowest energy orbital in a principal energy
state
Spherical
Orbitals increase in size with increasing
principal quantum number, n.
l = 0, ml = 1 orientation
1 orbital/subshell per energy level

105
l = 1, p orbitals
Each principal energy state above n = 1 has 3 p orbitals
ml = -1, 0, +1
Each of the 3 orbitals point along a different axis
px, py, pz
2nd lowest energy orbitals in a principal energy state
Two-lobes with a node at the nucleus, total of n nodes
High probability
of
Electron density & probability
finding an
electron of finding an electron, depends
Low probability on both distance & direction
of from the center of the atom.
finding an
electron

107
l = 2, d orbitals
• 3rd lowest energy orbitals in a principal energy state

• for n = 3 & l = 2 has 5 d orbitals

– ml = -2, -1, 0, +1, +2

• 4-lobes of the 5 orbitals are aligned in a different plane

– dxy, dyz, dxz, dx squared – y squared

– the fifth is aligned with the z axis, dz squared (two-lobed with a

toroid)

110
d orbitals

112
l = 3, f orbitals
 4th energy orbitals in a principal energy state
 for n = 4 & l = 3 has 7 f orbitals
 ml = -2, -1, 0, +1, +2
 f sub-level takes up to 14 electrons

113
 Electron Orbital Shape and Orientations (s, p,
d and f orbitals)
Spin Quantum Number, ms

In the 1920s, it was

discovered that two
electrons in the same orbital
do not have exactly the same
energy.

This led to a fourth quantum

number, the spin quantum
number, ms.
The spin quantum number, ms
 Spinning electrons generate magnetic fields, hence
+½ and -½ spin quantum numbers for the clockwise
& anticlockwise spins respectively.

 This implies that electrons are in are able to pair up,

though they repel each other due to the
electromagnetic force.

 Each orbital can therefore hold a maximum of 2

electrons.
ms = +½ ms = -½

117
Energy Shells and Subshells

118
How many 2p orbitals are there in an atom?

How many electrons can be placed in the 3d

subshell?

119
Total number of orbitals & electrons per energy level
• Easy way for total # of orbitals is to use n2.
e.g. 3rd energy level (n=3) has 3 sub-levels; s with 1, p with 3 and d
with 5 orbitals. Total is 1+3+5=9. Formula n2 = 32 = 9.

• Easy way for total # of electrons is to use 2n2.

e.g. 3rd energy level with s, p and d sublevels can take up to 2, 6 and
10 electrons. 2+6+10=18.
Formula 2n2 = 2x32 =18.
Orbitals and electron capacity of the 1 st
four energy levels

Orbitals with the same

value of n form a shell.
Different orbital types within
a shell are subshells.
Electron Configuration (EC)
Electron configuration is the distribution of electrons of an
atom among various atomic orbitals & energy levels.
EC Notation; uses quantum #s n
&l
For example, the electron
configuration of neon atom is
1s2 2s2 2p6.

Energy level = principal quantum #, n

Type of orbital = angular momentum quantum #
Number of electrons = atomic #, Z
Energies of Orbitals
3 Rules for Filling Electron Orbitals
Aufbau Principle
• Electrons are added one at a time to the lowest energy orbitals
available until all the electrons of the atoms have been accounted for.
Pauli Exclusion Principle
• An orbital can hold a maximum of two electrons. To occupy the same
orbital, two electrons must spin in the opposite direction.
Hund's Rule
• If two or more orbitals of equal energy are available, electrons will
occupy them singly before filling orbitals in pairs.
Pauli Exclusion Principle
• No two electrons in the same atom
can have the exact same quantum numbers.

• The quantum state is specified by the

four quantum numbers; no two
electrons can have the same set of
quantum numbers (ms = + or -)
Hund’s Rule
• Every orbital in a subshell is singly occupied with one electron
before any one orbital is doubly occupied, and all electrons in
singly occupied orbitals have the same spin.
Types of Electron Configurations

Spectroscopic, shorthand & orbital diagram notations

Spectroscopic notation:
– e.g. N (7e-s) - 1s22s22p3.

Shorthand notation: EC written in terms of noble gas that is closest to it, with a
fewer # of e-s
– e.g. N – [He]2s22p3.

For atom in period n, take noble gas from preceding period (n-1) [or with fewer
electrons] then add ns and other orbitals following energy order
Orbital Diagrams
• Orbital diagrams are a shorthand way to illustrate the energy levels of electrons.
• Each box in the diagram represents one orbital.
• Orbitals on the same subshell are drawn together.
• Arrows represent the electrons.
• The direction of the arrow represents the relative spin of the electron (+ or -).
Electron Configurations

130
Energies of Orbitals
• Orbital diagrams can also be drawn
vertically to illustrate increasing
energy.
• To complete an orbital diagram you
must first know how many electrons
the atom has.
• In a neutral atom:
# of electrons = # of protons
• so the # of electrons will be the same
as the atomic number.
Practice Question

Draw the Orbital Diagram and Write the

Ground State Electron Configuration of
magnesium, chlorine, and iron.

132
Valence Electrons
• The electrons in all the subshells within the highest principal energy
shell are called the valence electrons

• Electrons in lower energy shells are called core electrons

• Chemists have observed that one of the most important factors in the
way an atom behaves, both chemically and physically, is the number of
valence electrons.

133
The Periodic Table & EC

• Group number corresponds to the number of valence electrons

• Length of each “block” is the maximum number of electrons the

sublevel can hold

• Period number corresponds to the principal energy level of the

valence electrons

134
135
 s1
s2 p 1 p 2 p 3 p 4 p 5 s2
1
2 p6
3 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10
4
5
6
7
f2 f3 f4 f5 f6 f7 f8 f9 f10 f11 f12 f13 f14 f14d1

136
The Periodic Table & EC

1A 8A
1 2A 3A 4A 5A 6A 7A
2 Ne
3 3s2 P
4 3p3
5
6
7

P = [Ne]3s23p3
P has 5 valence electrons

137
The Periodic Table & EC
1A 8A
1 2A 3A 4A 5A 6A 7A
2
3 3d10 Ar
4 4s2 As
5 4p3
6
7

As = [Ar]4s23d104p3
As has 5 valence electrons

138
Practice – Use the Periodic Table to write the
short electron configuration and orbital
diagram for each of the following

• Na (atomic no. 11)

• Te (atomic no. 52)

• Tc (atomic no. 43)

139
EC & Elements Properties

Elements in same groups, with same

chemical properties have same valence
number, hence very similar electron
configurations
EC & Elements Properties
• # of valence electrons largely determines the behavior of an element (chemical and some physical)

• Since # of valence electrons follows a Periodic pattern, the properties of the elements should also
be periodic

• Quantum mechanical calculations show that 8 valence electrons should result in a very unreactive
atom, an atom that is very stable – and the noble gases, that have 8 valence electrons are all very
stable and unreactive

• conversely, elements that have either one more or one less electron should be very reactive – and
the halogens are the most reactive nonmetals and alkali metals the most reactive metals
– as a group

141
Group Names - EC
Stability

Elements of varying stability fall

into one of 3 categories.
The most stable atoms have
completely full energy levels.
~Full Energy Level
~Full Sublevel (s, p, d, f)
~Half Full Sublevel ( d5, f7)
 Stability

Next in order of stability are

elements with full sublevels.
~Full Energy Level
~Full Sublevel (s, p, d, f)
~Half Full Sublevel ( d5, f7)
Stability

Finally, the elements with

half full sublevels are also stable,
but not as stable as elements with
completely full energy levels or sublevels.
~Full Energy Level
~Full Sublevel (s, p, d, f)
~Half Full Sublevel ( d5, f7)
Electron Configurations Exceptions

There are basic exceptions in

electron configurations in the
d- and f-sublevels.

These fall in the circled

areas on the table below.
Electron Configurations Exceptions
Chromium
Expected: [Ar] 4s2 3d4 Actual: [Ar] 4s1 3d5

For some elements, in order to exist in a more stable state, electrons

from an s sublevel will move to a d sublevel, thus providing the
stability of a half-full sublevel.

To see why this can

happen we need to
examine how "close" d
and s sublevels are.
Electron Configurations Exceptions

Because of how close the f & d orbitals are

to the s orbitals, very little energy is
required to move an electron from the s
orbital (leaving it half full) to the f or d
orbital, causing them to also be half full.

(It's kind of like borrowing a

cup of sugar from a neighbor).
Electron Configurations Exceptions
Copper
Expected: [Ar] 4s2 3d9 Actual: [Ar] 4s1 3d10

Copper gains stability when an electron from the 4s orbital fills the 3d orbital.
Exceptional ECs

• Others with 5s and 4d energy levels very close

Nb: [Kr]5s14d4
Ru: [Kr]5s14d7
Rh: [Kr]5s14d8
Pd: [Kr]5s04d10
 EC & Ion Charge

• Ion: electron goes out of an atom for positively charged species (cations) e.g. 1s2
for Li+OR electrons enter an atom for negatively charged species (anions) e.g.
1s22s22p6 for F-1.
• Many metals and nonmetals form one ion, and that the charge on that ion is
predictable based on its position on the Periodic Table
Group 1A = +1, Group 2A = +2,
Group 7A = -1, Group 6A = -2, etc.
• These atoms form ions that will result in an electron configuration that is the same
as the nearest noble gas
• Isoelectronic: having identical electronic configurations e.g. F-1 and Ne both have
10 electrons; 1s22s22p6

151
152
Concepts pertaining to Schrodinger's Wave Equation
Paramagnetic: net magnetic fields reinforce one another; have at least one
unpaired spin.
• Substances are attracted by a magnet.
• All atoms with odd # of electrons are paramagnetic.
• Some atoms with even # of electrons are paramagnetic – draw orbital diagram
EC to know.
Diamagnetic: magnetic fields are anti-parallel to each other (all electron spins
are paired).
• Substances are repelled by a magnet
• For some atoms with even # of electrons .
EC of Anions in their Ground State
• Anions are formed when atoms gain enough electrons to have 8 valence
electrons
• filling the s and p sublevels of the valence shell
• The sulfur atom has 6 valence electrons
S atom = 1s22s22p63s23p4
• In order to have 8 valence electrons, it must gain 2 more
S2- anion = 1s22s22p63s23p6

154
EC of Cations in their Ground State
• Cations are formed when an atom loses all its valence electrons
resulting in a new lower energy level valence shell
however the process is always endothermic

• The magnesium atom has 2 valence electrons

Mg atom = 1s22s22p63s2

• When it forms a cation, it loses its valence electrons

Mg2+ cation = 1s22s22p6

155
THANK YOU