CHM 101: INTRODUCTORY PHYSICAL CHEMISTRY (3 Units)

Atoms, molecules and structures. Electronic configuration.

Periodicity and building up of the periodic table.

Chemical reactions, chemical equations and stoichiometry.

Bonding and intermolecular forces.

Kinetic theory of matter; derivation and calculation of all the

laws involved.

Thermochemistry and simple calculations based on Hess’s

law. Rate of reaction.Chemical equilibrium.

Oxidation-Reduction reaction.

Chemical kinetics, equilibra and related simple calculation

Important applications of equilibra like pH, Solubility.

Solubility of ionic solids.
Electrochemistry and workings of various cells, Corrosion.
Atomic Structure

History of Atomic Theory

 Democritus (460 - 370 BC)

• Was the first person to come up with the idea of

atom
• Believed that all matter was composed of
indivisible particles he called “ATOMS”
• Which is derived from the Greek word “Atomos” –
meaning indivisible
• He also believed that different atoms:
– Are different sizes
– Have different properties
• Other philosophers of that time did not agree
with his theories.
 John Dalton (1766-1844)
• Dalton is the “Father of
Atomic Theory”
• Dalton’s ideas were so
brilliant that they have
remained essentially
intact up to the present
time and has only been
slightly corrected.
 Dalton’s Atomic Theory (1803)
aka: 5 Postulates

1. All matter is composed of extremely small

particles called atoms. (I agree with Democritus!)
2. All atoms of a given element are
identical, having the same:
- size
- mass
- chemical properties.
3. All atoms of different elements are
different.
 Dalton’s Atomic Theory (1803)
aka: 5 Postulates
4. Atoms cannot be created, divided into
smaller particles, or destroyed.
**In a chemical reaction, atoms of different elements
are separated, joined or rearranged. They are
never changed into the atoms of another element.
We will learn more later**
5. Atoms combine in definite whole
number ratios to make compounds
(you can’t have a ½ of a Carbon bonding with Oxygen; it’s
a whole atom or no atom)
 Dalton’s Atomic Model
•Based on Dalton’s Atomic
Theory (5 postulates), most
scientists in the 1800s believed
that the atom was like a tiny
solid ball that could not be
broken up into parts.
•Dalton was credited for the
three Atomic Laws that were
proven after his time.
 Dalton’s Atomic Laws
1. Law of Conservation of Mass
Matter cannot be created or
destroyed in any physical or
chemical process, just transferred.
2. Law of Constant Composition
When atoms combine to form molecules,
the ratio of atoms is constant.
Example – H2O will always have 2 times
as many Hydrogen atoms as Oxygen.
 Dalton’s Atomic Laws
3. Law of Multiple Proportions – if two
elements can combine to form more than one
compound, then the ratio of the second element
combined with a certain mass of the first element
is always a ratio of small whole numbers.

Example:
CO vs. CO2
Formula

Ratio of N:O
 The Law of Conservation of Mass

•When a chemical reaction occurs,

mass is neither created nor
destroyed but only changed.
 JJ Thomson (1856-1940)

• Used cathode rays to

prove that Dalton’s Solid-
ball model could be
broken into smaller
particles
•Thomson is credited
with discovering
electrons
 Cathode Ray Tubes
• Cathode rays had been used for
some time before Thompson’s
experiments.
• A cathode ray is a tube that has
a piece of metal, called an
electrode, at each end. Each
electrode is connected to a power
source (battery).
• When the power is turned on, the electrodes
become charged and produce a stream of charged
particles. They travel from cathode, across the tube
to the anode.
 Cathode Ray Tubes
• Thomson put the tube in
a magnetic field. He -----------------------------
predicted that the
stream would travel in a
straight path. ++++++++++++++
• Instead, he found that
the path curved away •Like charges repel each other,
from a negatively and objects with unlike charges
charged plate and attract each other, Thomson
toward a positively concluded that the stream of
charged plate charged particles had electrons
• Why? in them.
 Cathode Ray Tube Experiment

•Thompson Concluded:
•Cathode rays are made up of
invisible, negatively charged
particles called Electrons.
•These electrons had to come from the matter (atoms)
of the negative electrode.

•Since the electrodes could be made from a variety of

metals, then all atoms must contain electrons!
 Thomson’s Plum Pudding Model
•Thomson’s Plum Pudding model is a +
charge sphere that has (- )charged
electrons scattered inside, like “raisins” in
“plum pudding”.
•Overall, the atom is neutral atom
because the atom had the same number
of positive and negative charges.
•From Thomson’s experiments, scientists concluded that
atoms were not just neutral spheres, but somehow were
composed of electrically charged particles.
•The balance of positive and negative charge supports the
neutral atom.
 Rutherford (1871-1937)

• Took Thomson’s Plum

Pudding Model and added to
it
• Used the “Gold Foil
Experiment” to discover the
existence of:
– An atomic Nucleus
– Protons (in later experiments)
• You must be able to explain
the Gold Foil Experiment…it
will be on the CST
 Gold Foil Experiment

• Rutherford directed a narrow

beam of alpha particles (+
charges) at a thin piece of gold
foil.

• Based on observations from

other experiments involving
alpha particles, he predicted
that the (+) charges would go
through the foil
 Results from Gold Foil Experiment

•Rutherford found that

every once and a while, a
+ particle was deflected
bounced back. (about 1%
of the time)
•Why?
•Because the + charge hit
a central mass of positive
charge and was repelled.
The Gold Foil Experiment
 The Nuclear Model of the Atom

•To explain the results of the

experiment, Rutherford’s team proposed
a new model of the atom.
 Conclusions from Rutherford’s Gold Foil
Experiment (memorize this!)

• The atom contains a positively

charged “nucleus”
•This nucleus contains almost all of the
mass of the atom, but occupies a very
small volume of the atom.
•The negatively charged electrons
occupied most of the volume of the atom.
• The atom is mostly empty space.
 Rutherford’s Planetary Model

• To explain his
observations,
Rutherford developed a
new model
•The electrons orbit
the nucleus like the
planets revolve around
the sun.
 Bohr (1885-1962)

• Worked in Rutherford’s lab

• Wondered why – electrons are
not attracted to the + nucleus
and cluster around it
• Disproved Rutherford’s
Planetary Model
• Experimented with light and
its interaction with matter to
develop a new model.
 Bohr’s Energy Level Model
Energy Level Model: Electrons are
arranged in circles around the
nucleus. Each circle has a different
energy.
•Electrons are in constant motion,
traveling around the circle at the
speed of light.
•Electrons can “jump” from one circle
to the next
•But they can’t go to the nucleus they
traveling too fast to be fully attracted.
 Bohr’s Energy Level Model

 He proposed the following:

1. Protons and neutrons are in the nucleus
2. Electrons can only be certain distances
from the nucleus.
3. The electrons orbit the nucleus at fixed
energy levels.
4. The electrons must absorb or emit a
fixed amount of energy to travel between
these energy levels
 Review
Who is the father of atomic theory?
Dalton
What was the first model of the atom?
Dalton’s Tiny Ball Model
What are Dalton’s 3 Laws?
Law of Conservation of Mass, Law of Constant
Composition, Law of Multiple Porportion
 Review
How were Thomson’s and Dalton’s model
different?
Dalton’s model was 1 sphere that cannot be
divided, Thomson had the plum pudding where
electrons are randomly spread throughout a
positively charged sphere.
What did Thomson find out?
Atoms have electrons, they have a - charge
 Review
What were Rutherford’s conclusions from the Gold
Foil Experiment?
• Atom has a positively charged nucleus
• electrons are outside,
• atoms are mostly empty
• Nucleus contains most of the mass.
 Atomic Structure and Periodicity

• Electromagnetic Radiation
Radiant energy that exhibits wavelength-like
behavior and travels through space at the
speed of light in a vacuum.
• Example: The sun light, energy used in
microwave oven, the x-rays used by doctors.
 Waves
Waves have 3 primary characteristics:
 Wavelength (): distance between two
consecutive peaks in a wave.
 Frequency (): number of waves (cycles) per
second that pass a given point in space.
 Speed: speed of light is 2.9979  108 m/s. We
will use 3.00 x108 m/s.
The Nature of Waves
 Wavelength and frequency can be interconverted
and they have an inverse relationship


 = c/
 = frequency (s1)
 = wavelength (m)
c = speed of light (m s1)
• Wavelength is also given in nm (1 nm = 10-9 m)
and Angstroms (Å) (1 Å = 10-10 m).
• The frequency value of s1 or 1/s is also called
“hertz (Hz)” like KHz on the radio.
Classification of Electromagnetic Radiation
Example: When green light is emitted from an
oxygen atom it has a wavelength of 558 nm.
What is the frequency?
We know,
 = c/ where, c = speed of light
= 3.00 x 10 8m/s
10m
8
3.00 / s
   = wavelength
5.58 10 7
m
14  1
= 558 nm
 5.38 10s (need to convert in m)
14 9
7
 5.38 10Hz 558nm 
10m
 5.58 10m
1nm
 Planck’s Constant
• Transfer of energy is quantized, and can only
occur in discrete units, called quanta.

hc
 E = h =


E = change in energy, in J
h = Planck’s constant, 6.626  1034 J s
 = frequency, in s1
 = wavelength, in m
 • Example: The Blue color in fireworks is often achieved by
heating copper (I) chloride (CuCl) to about 1200oC. Then the
compound emits blue light having a wavelength of 450 nm.
What is the increment of energy (the quantum) that is emitted
at 4.50 x 102 nm by CuCl?
The quantum of energy can be calculate from the equation


E = h
The frequency  for this case can be calculated as follows:
 

8 
c 2.9979 10m / s



  
14

 6.66 10s 1
 4.50 10m
7

So,
E = h = (6.626 x 10-34J.s)(6.66 x 1014 s-1)
= 4.41 x 10-19J
A sample of CuCl emitting light at 450 nm can only lose energy in
increments of 4.41 x 10-19J, the size of the quantum in this case.
 Energy and Mass
• According to Einstein theory of relativity-
Energy has mass; Einstein equation,
E = mc2 where, E = energy, m = mass
c = speed of light
• After rearrangement of the equation,
E
m 2
c
Now we can calculate the mass associated
with a given quantity of energy
 • Einstein suggested that electromagnetic
radiation can be viewed as a stream of
“particles” called photons. The energy of each
photon is given by,
hc
E photon = h =




E hc / 


h
mphoton = 2 = =
c c 2
c
• It was Einstein who realized that light could not
be explained completely as waves but had to
have particle properties. This is called the dual
nature of light.
Electromagnetic Radiation
 Wavelength and Mass
• de Broglie thought if waves like light could have particle
properties that particles like electrons could have wave
properties. We have,

  velocity 
h h
m  m 
c 
de Broglie’s equation, h
 =
m
 = wavelength (m); m = mass (kg);  = velocity (m/s)
h = Planck’s constant, 6.626  1034 J s = kg m2 s1

• This equation allows us to calculate the wavelength of a

particle. Matter exhibits both particulate and wave
properties.
• Example: Compare the wavelength for an electron
(mass = 9.11 x 10-31 kg) traveling at a speed of 1.0 x 107
m/s with that for a ball (mass = 0.10 kg) traveling at 35
m/s.
We use the equation  = h/m, where
h = 6.626  1034 J.s or 6.626  1034 kg m2 /s
since, 1 J = 1 kg. m2 /s2
For the electron,



 34 kg.m.m
6.626 10
 s   11
e   7.27  10 m
9.11 10 kg1.0  10 m / s
 31


 7



For the ball,  34 kg.m.m

6.626  10 34
 b  s  1.9  10 m
0.10 kg  35 m / s
 Atomic Spectrum of Hydrogen
• When H2 molecules absorb energy, some of the H-H
bonds are broken and resulting hydrogen atoms are
excited. The excess energy is released by emitting light of
various wavelengths to produce the emission spectrum of
hydrogen atom.
• Continuous spectrum: Contains all the wavelengths of
light.
Line (discrete) spectrum: Contains only some of the
wavelengths of light. Only certain energies are allowed,
i.e., the energy of the electron in the hydrogen atom is
quantized. hc
 E = h =

















































A Continuous Spectrum (a) and A Hydrogen Line Spectrum (b)

A Change between Two Discrete Energy Levels
 The Bohr Model
• The electron in a hydrogen atom moves around the
nucleus only in certain allowed circular orbits. The
energy levels available to the hydrogen atom:

E =  2.178 10 J (z /n )
18 2 2
E = energy of the levels in the H-atom
z = nuclear charge (for H, z = 1)
n = an integer, the large the value, the larger is the
orbital radius.
• Bohr was able to calculate hydrogen atom energy levels
that exactly matched the experimental value. The
negative sign in the above equation means that the
energy of the electron bound to the nucleus is lower
than it would be if the electron were at an infinite
distance.
 Quantum Theory

Fig. 1.2 Part of the emission spectrum of hydrogen.

Dr. S. M. Condren
 Quantum Theory
For the Balmer series
 = 1/ = R(1/22 - 1/n2)
where R => Rydberg constant for hydrogen,
1.097 x 107m-1
For the Lyman series
 = 1/ = R(1/12 - 1/n2)

Dr. S. M. Condren
Electronic Transitions in the Bohr Model for the Hydrogen Atom
 Quantum Mechanics
Based on the wave properties of the atom
Schrodinger’s equation is (too complicated to be
detailed here),
H = E
 = wave function 
= mathematical operator
H
E = total energy of the atom
A specific wave function is often called an orbital.
This equation is based on operators – not simple
algebra. This is a mathematical concept you will not
have dealt with yet.
Radial Probability Distribution
 Quantum Numbers (QN)
When we solve the Schrodinger equation, we find many
wave functions (orbitals) that satisfy it. Each of these
orbitals is characterized by a series of numbers called
quantum numbers, which describe various properties of
the orbital.
1. Principal QN (n = 1, 2, 3, . . .) - related to size and
energy of the orbital.
2. Angular Momentum QN (l = 0 to n  1) - relates to
shape of the orbital. l = 0 is called s; l = 1 is called p; l = 2
is called d; l = 3 is called f.
3. Magnetic QN (ml = l to l including 0) - relates to
orientation of the orbital in space relative to other
orbitals.
4. Electron Spin QN (ms = +1/2, 1/2) - relates to the spin
states of the electrons.
Example: For principal quantum level n = 5,
determine the number of allowed subshells
(different values of l), and give the designation of
each.
For n = 5, the allowed values of l run from 0 to 4
(n – 1 = 5 – 1). Thus the subshells and their
designations are

l=0 l=1 l=2 l=3 l=4

5s 5p 5d 5f 5g
 Orbital Shapes and Energies
Two types of representations for the hydrogen
1s, 2s and 3s orbitals are shown below. The s
orbitals are spherical shape.

Two Representations of the

Hydrogen 1s, 2s, and 3s Orbitals
 Representation of p orbitals
The p orbitals are not spherical like s orbital but have two
loves separated by a node at the nucleus. The p orbitals are
labeled according the axis of the xyz coordinate system.

The Boundary Surface Representations of All Three 2p Orbitals

 Representation d orbitals

The five d orbital shapes are shown below. The d

orbitals have two different fundamental shapes.

The Boundary Surfaces of All of the 3d Orbitals

 Energy Diagram for Hydrogen Atom
The energy of a particular orbital is determined by its value
of n. All orbitals with the same value of n have the same
energy and are said to be degenerate. Hydrogen single
electron occupy the lowest energy state, the ground state.
If energy is put into the system, the electron can be
transferred to higher energy orbital called excited state.

Orbital Energy
Levels for the
Hydrogen Atom
 Pauli Exclusion Principle

• In a given atom, no two electrons can have the

same set of four quantum numbers (n, l, ml, ms).

• Therefore, an orbital can hold only two

electrons, and they must have opposite spins.
 Polyelectronic Atoms
• For polyelectronic atoms in a given principal
quantum level all orbital are not in same energy
(degenerate). For a given principal quantum level
the orbitals vary in energy as follows:

Ens< Enp < End < Enf

• In other words, when electrons are placed in a

particular quantum level, they prefer the orbital
in the order s, p, d and then f.
 Aufbau Principle

As protons are added one by one to the

nucleus to build up the elements, electrons are
similarly added to these hydrogen-like orbitals.

H : 1s1, He : 1s2, Li : 1s2 2s1, Be : 1s2 2s2

B : 1s2 2s2 2p1, C : 1s2 2s2 2p2.
 Hund’s Rule
The lowest energy configuration for an atom is
the one having the maximum number of
unpaired electrons allowed by the Pauli
principle in a particular set of degenerate
orbitals.

N : 1s2 2s2 2p3, O : 1s2 2s2 2p4,

F : 1s2 2s2 2p5, Ne : 1s2 2s2 2p6,
Na : 1s2 2s2 2p63s1 OR [Ne] 3s1
The Electron Configurations in the Type of
Orbital Occupied Last for the First 18 Elements
 Valence Electrons
The electrons in the outermost principle
quantum level of an atom.
Atom Valence Electrons
Ca 2
N 5
Br 7
Valence electron is the most important electrons
to us because they are involved in bonding.
Elements with the same valence electron
configuration show similar chemical behavior.
Inner electrons are called core electrons.
Electron Configurations for Potassium Through Krypton
The Orbitals Being Filled for Elements in Various Parts of the Periodic Table
The Periodic Table With Atomic Symbols, Atomic
Numbers, and Partial Electron Configurations
 Broad Periodic Table Classifications

• Representative Elements (main group): filling s

and p orbitals (Na, Al, Ne, O)
• Transition Elements: filling d orbitals (Fe, Co, Ni)
• Lanthanide and Actinide Series (inner transition
elements): filling 4f and 5f orbitals (Eu, Am, Es)
The Order in which the Orbitals Fill in Polyelectronic Atoms
 Ionization Energy

The quantity of energy required to remove an

electron from the gaseous atom or ion.

X(g) X+ (g) + e-
where, the atom or ion is assumed to be in its
ground state.
 Periodic Trends

First ionization energy:

increases from left to right across a
period;
decreases going down a group.
The Values of First Ionization Energy for
The Elements in the First Six Periods
Trends in Ionization Energies
for the Representative Elements
 Electron Affinity

The energy change associated with the addition

of an electron to a gaseous atom.
X(g) + e 
 X(g)
These values tend to be exothermic (energy
released). Adding an electron to an atom causes
it to give off energy. So the value for electron
affinity will carry a negative sign.
The Electronic Affinity Values for Atoms Among the
First 20 Elements that Form Stable, Isolated X- Ions
 Periodic Trends
Atomic Radii: Atomic radii can be obtained by
measuring the distances between atoms in
chemical compounds and atomic radius is assumed
to be half this distance.
• Decrease going from left to right across a period.
This decrease can be explained in terms of the
increasing effective nuclear charge in going from
left to right. The valence electron are drawn closer
to the nucleus, decreasing the size of the atom.
• Increase going down a group, because of the
increase in orbital sizes in successive principal
quantum levels.
The Radius of an Atom
Atomic Radii for Selected Atoms
 Information Contained
in the Periodic Table
1. Each group member has the same valence electron
configuration. Group elements exhibit similar chemical
properties.
2. The electron configuration of any representative element
can be obtained from periodic table. Transition metals –
two exceptions, chromium and copper.
3. Certain groups have special names (alkali metals,
halogens, etc).
4. Metals and nonmetals are characterized by their chemical
and physical properties. Many elements along the division
line exhibit both metallic and non metallic properties
which are called metalloids or semimetals.
Special Names for Groups in the Periodic Table
 Summary
• Electromagnetic Radiation: Wavelength like
behavior.
• Frequency,  = c/ ( = wavelength, c = speed of
light).
• Energy Transfer, E = h = hc/

• de Broglie’s Equation:  = h/m
• The Bohr Model: electron in a hydrogen atom moves
around the nucleus only in certain allowed circular
orbits.

• Quantum Mechanics: H= E
• Heisenberg Uncertainty Principle: Position and
momentum cannot be determined precisely at a
given time.
• Quantum Numbers: Principal QN, Angular
momentum QN, Magnetic QN, an Electron Spin
QN.
• Orbital Shapes and Energies: s, p, and d orbitals.
• Pauli Exclusion Principle:
• Aufbau Principle:
• Hund’s Rule:
• Periodic Table:
• Ionization Energy:
• Electron Affinity:
• Periodic Trends: