INTRODUCTION TO TO

INTRODUCTION
PHYSICAL CHEMISTRY
PHYSICAL CHEMISTRY
Objectives:
CHE232
• Discuss the importance and history of Physical
Chemistry.
• Describe how matter behaves on a molecular and
atomic level including how chemical reactions
occur.
• Describe the physical structure of chemical
compounds, the way they react with other matter
and the bonds that hold their atoms together.
• Evaluate the basic principles of Ideal Gas Equation
and other Gas Laws.
What is Physical Chemistry?
is the study of the underlying physical principles that
govern the properties and behavior of chemical systems. A

“The physics that supports chemistry” – Atkins, Peter

“The HOW and the WHY of chemistry” – de Paula, Julio

“The numbers that explains the things that happen in chemistry” – Keller, James

QUANTITATIVE SCIENCE !
Why Do we study Physical Chemistry?
Areas of Physical Chemistry
Chemical systems

microscopic macroscopic
State and Properties of Systems
State of the system:
The present status of the system described in terms of properties such as
pressure, temperature, and volume are called the state of system.
Properties of the system:
The characteristics by which the physical condition of the system is
described are called as properties of system.
Some examples of these characteristics are temperature, pressure, volume
etc. and are called as properties of system.
The system properties are of two types: extensive and intensive
properties.
Properties of Chemical Systems
Extensive properties of system
The properties of the system that depend on the mass or quantity of
the system are called extensive properties. Some examples of
extensive properties are mass, volume, enthalpy, internal energy,
entropy etc.
Intensive properties of the system
These properties do not depend on the quantity of matter of the
system. Some of the examples of intensive properties are freezing
point temperature, boiling point, temperature of the system, density,
specific volume etc.
States (Phases) of Matter
Solid phase, individual particles of the
material are bound densely together in fixed
positions by strong attractive forces, so that
the solid holds its shape.
Liquid phase, attractive forces are weaker, so
particles of the material can slide past one
another.
Gas phase, attractive forces are extremely
weak, so particles are widely separated.

Liquids assume the shape of the container that holds them but do not expand
to fill the entire volume of the container.
Gases will completely fill the shape and volume of a container.
External Forces Applied
The particles of any substances are constantly in motion, but their energy
levels vary.
Particles of gases have much greater kinetic energy (energy of motion)
than those of liquids, which in turn have more energy than solids.
Heating materials will increase their kinetic energy. If enough energy is
added to a substance, the particles will overcome their attractive forces
and the material will change to a less ordered state: A solid will melt into a
liquid, or a liquid will evaporate into a gas.
When materials cool, they lose kinetic energy: Gases condense into
liquids, and liquids freeze into solids
Gas Laws
Charles’s law Boyle’s law
Gas Laws
Gay-Lussac’s law Avogadro’s law
Combined Gas Law
Problem 1:
A fixed mass of gas was placed in a gas syringe at 10°C and
101 kPa and found to have a volume of 43 cm3. What would
be its volume if the pressure was increased to120 kPa and
the temperature to 80°C ?
Problem 2:
A sample of hydrogen gas was found to have a
pressure of 125 kPa when the temperature was 23°C.
What can its pressure be when the temperature is
11°C?
Problem 3:
A perfect gas undergoes isothermal compression,
which reduces its volume by 1.80 dm3. The final
pressure and volume of the gas are 1.97 bar and 2.14
dm3, respectively. Calculate the original pressure of
the gas in (a) bar, (b) Torr.
Perfect Gases (Ideal Gases)
A hypothetical gas, one in which all collisions between atoms or
molecules are perfectly elastic and in which there are no
intermolecular attractive forces.
Ideal gas can be characterized by three
state variables: absolute pressure (P),
volume (V), and absolute temperature
(T).

Ideal gas is modelled on the Kinetic

n = number of moles
T = temperature in K
V = volume in m3
P = pressure in Pa
R = universal gas constant = 8.3145 J/mol K
Ideal Gas Law
PV = nRT
M = m/n ∴ n = m/M
PV = mRT/M
ρ = m/V
P = ρRT/M
Temperature and Pressure Conditions
Condition T P
STP 0°C 1.00 atm
NTP 20°C 1.00 atm
SATP 25°C 1.00 atm
Problem 4:
What is the pressure of a 500 cm3 tube of methane
(CH4) if 4.6 g of the gas are present at a temperature
of 45°C ?
Problem 5:
A homeowner uses 4.00 × 103 m3 of natural gas in a
year to heat a home. Assume that natural gas is all
methane, CH4, and that methane is a perfect gas for
the conditions of this problem, which are 1.00 atm
and 20°C. What is the mass of gas in grams used?
Problem 6:
What mass of oxygen is in a 2 dm3 container at STP?
Ideal Gas Mixtures and Dalton’s Law
n = n1 + n2 + . . .
P = (n1 + n2 + . . .) RT/V
= n1RT/V + n2RT/V + . . .
= P1 + P2 + . . . = σ𝑖 𝑃𝑖

Where:
P1 : partial pressure of species 1
P2 : partial pressure of species 2
The partial pressure of a gas in an ideal gas mixture is the pressure
that it would exert alone in the total volume at the temperature of
the mixture:
Pi = niRT/V
replacing RT/V with P/n:
Pi = niP/n = yiP
Where: Pi = partial pressure of species i
ni = number of moles of species i
R = universal gas constant
V = volume of gases
T = temperature of gases
P = total pressure of gases
n = total moles of gases
yi = mole fraction of species i
Problem 7:
A mixture of 1 mol of methane and 3 mol of ethane
is held at a pressure of 10 bar. What are the mole
fractions and partial pressures of the two gases?
Problem 8:
A certain mixture of He and Ne in a 356-cm3 bulb
weighs 0.1480 g and is at 20.0°C and 748 torr. Find
the mass and mole fraction of He present and the
partial pressures of He and Ne.
Problem 9:
A certain mixture of N2 and O2 has a density of 1.185 g/L at
25°C and 101.3 kPa. Find the mole fraction and partial
pressure of O2 in the mixture.
Problem 10:
The mole fractions of the main components of dry air at sea
level are xN2 = 0.78, xO2 = 0.21, xAr = 0.0093, xCO2 = 0.0004.
(a) Find the partial pressure of each of these gases in dry air
at 1.00 atm and 20°C. (b) Find the mass of each of these
gases in a 15 ft × 20 ft × 10 ft room at 20°C if the
barometer reads 740 torr and the relative humidity is zero.
Also, find the density of the air in the room. Which has a
greater mass, you or the air in the room of this problem?
Kinetic-Molecular Theory
The assumptions or postulates are:
1. Gases are composed of molecules that are in continuous motion, travelling in
straight lines and changing direction only when they collide with other
molecules or with the walls of a container.
2. The molecules composing the gas are negligibly small compared to the
distances between them.
3. The pressure exerted by a gas in a container results from collisions between
the gas molecules and the container walls.
4. Gas molecules exert no attractive or repulsive forces on each other or the
container walls; therefore, their collisions are elastic (do not involve a loss of
energy).
5. The average kinetic energy of the gas molecules is proportional to the kelvin
temperature of the gas.
Root-Mean-Square Velocities of Gaseous Particles
Measuring the velocities of particles at a given time results in a large
distribution of values; some particles may move very slowly, others very quickly,
and because they are constantly moving in different directions, the velocity
could equal zero. To properly assess the average velocity, average the squares of
the velocities and take the square root of that value. This is known as the root-
mean-square (RMS) velocity, and it is represented as follows:

3𝑅𝑇
νത = ν𝑟𝑚𝑠 = 𝑀

Where: R is the gas constant, T is absolute temperature, and Mm is the molar mass of the gas particles in kg/mol.

1
Kinetic Energy of Gases: 𝐾𝐸 = 𝑚ത
ν 2
2
Problem 11:
What is the root-mean-square speed for a sample of
oxygen gas at 298 K?
Problem 12:
What is the root-mean-square speed for a sample of What
is the root mean square velocity of He atoms at room T,
25.0°C?
Maxwell-Boltzmann Distributions
The Maxwell–Boltzmann distribution is the statistical distribution of molecular
speeds in a gas. It corresponds to the most probable speed distribution in a
collisional-dominated system consisting of many non-interacting particles.
The number of molecules moving with velocity between ν and ν + dν is:

3 𝑚ν2
𝑚 [− ]
𝑓 ν = 𝑁( ) 2 𝑒 2𝑘𝑇
2𝜋𝑘𝑇
Where: m is the mass of the molecule.
N is the number of molecules
K is the Boltzmann constant
T is the absolute temperature