PHYSICAL CHEMISTRY 1

Dr. Ngo Thanh An

1
Introduction

• The principal goal of physical chemistry is to

understand the properties and behaviour of material
systems and to apply this understanding in useful
ways.

2
References

Textbook

3
Introduction

Thermodynamics:
phenomenological theory to
describe equilibrium properties
of macroscopic systems
based on few macroscopically
measureable quantities.
Or: The study of heat and its
transformation into mechanical
energy is called
thermodynamics.
4
Introduction

5
Definitions

6
Definitions

• Macroscopic system: A large system containing

many atoms or molecules
• Microscopic system: a system consisting of a single
atom or molecule
• Macroscopic properties (such as temperature and
pressure) apply only to a macroscopic system and
are properties of the whole system.
• Microscopic properties (such as kinetic energy and
momentum) are mechanical in nature.

7
Definitions

A body or system whose condition

is altered without gaining heat from
or losing heat to the surroundings
(energy is transferred only as work.)

8
Definitions
Thermodynamic definition of work: It is a kind of interaction that would occur at the
system boundaries. It can be positive or negative.
Heat: Heat is a mode of energy transfer that takes place between the system and the
surroundings solely due to the temperature difference. Thus, heat is a transient
phenomenon. It can be recognized only during a process.
Energy exists in many forms, such as mechanical energy, heat, light, chemical
energy, and electrical energy. Energy is the ability to bring about change or to do
work.

9
Definitions

A thermodynamic process is a passage of a

thermodynamic system from an initial state
to a final state 10
Definitions

When a gas is compressed or expanded so that no heat enters or

leaves a system, the process is said to be adiabatic.

Adiabatic changes of volume can be achieved by performing the

process rapidly so that heat has little time to enter or leave or by
thermally insulating a system from its surroundings.

Do work on a pump by pressing

down on the piston and the air is
warmed.

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Definitions

When a gas adiabatically expands, it does work on its surroundings

and gives up internal energy, and thus becomes cooler.

Blow warm air onto your hand from your wide-open mouth. Now
reduce the opening between your lips so the air expands as you blow.
Adiabatic expansion—the air is cooled.

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 Definitions

A source supplies
energy in the
form of heat, and
a sink absorbs it.

Bodies with relatively large thermal

masses can be modeled as thermal
energy reservoirs.
• A hypothetical body with a relatively large thermal energy capacity (mass x specific
heat) that can supply or absorb finite amounts of heat without undergoing any
change in temperature is called a thermal energy reservoir, or just a reservoir.
• In practice, large bodies of water such as oceans, lakes, and rivers as well as the
atmospheric air can be modeled accurately as thermal energy reservoirs because of
their large thermal energy storage capabilities or thermal masses.
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Definitions

• State Variables
• system quantity whose values are fixed at constant
temperature, pressure, composition
• State Function
• a system property whose values depends only on the initial
and final states of the system.
• Path Functions
• system quantity whose value is dependent on the manner
in which the transformation is carried out.

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Definitions

An intensive property is a bulk property, meaning that it is a physical property of

a system that does not depend on the system size or the amount of material in
the system. Ex: Temperature, Pressure, density, specific heat, …

By contrast, an extensive property is additive for independent, non-interacting

subsystems. The property is proportional to the amount of material in the system.
Ex: volume, mole number, mass, length, entropy, enthalpy, Gibbs free energy …

State 2
State
(x2,y2,z2)
function
(depending on state
variables)

State 1  State functions: Can we find the exact form of functions?

(x1,y1,z1)  We don’t need to know the functions because we just pay
(depending on state attention to the initial and final state.
variables)
 State 1 or state 2 is completely determined by the value of
its state functions at a certain set of state variables. 15
Definitions
State variables:
Describe equilibrium state of thermodynamic system uniquely.
Intensive: homogeneous of degree 0, independent of system size
Extensive: homogeneous of degree 1, proportional to system
size
Note: Intensive state variables serves as equilibrium parameters.
Ex: temperature (T), pressure (P) and chemical potential ().

--------------------------------------------
Euler's Theorem: Let f(x1,…,xn) be a function such that

f ( x1 ,...,  xn )  n f ( x1 ,..., xn )

Then f is said to be a homogeneous function of degree n. 16

Definitions
Intensive and extensive variables

17
Definitions
Definitions

• Gas - a substance that is characterised by widely

separated molecules in rapid motion
• Mixtures of gases are uniform. Gases will expand to
fill containers.
• Ex:
- Common gases include - O2 and N2, the major
components of "air"
- Other common gases - F2, Cl2, H2, He, and N2O
(laughing gas)

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Some state variables

• The pressure of a gas is best defined as the forces

exerted by gas on the walls of the container
• Define P = force/area
• The SI unit of pressure is the Pascal
• 1 Pa = N/m2 = (kg m/s2)/m2

Force
Pr essure 
Area

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Some state variables

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Some state variables

• How do we measure gas pressure?

• We use an instrument called the barometer -
invented by Torricelli
• Gas pressure conversion factors
• 1 atm = 760 mm Hg = 760 torr
• 1 atm = 101.325 kPa = 1.01325 bar
• 1 bar = 1 x 105 Pa (exactly)
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Some state variables

Definition: Temperature measures the degree of hotness of a body (“how

hot”). It doesn’t depend on the mass or the material of an object. It can be
thought of as a measure of the average kinetic energy of the atoms or
molecules in a body.

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Some state variables

If two thermodynamic systems are each in thermal equilibrium with a third,

then they are in thermal equilibrium with each other.

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Some state variables

As thermal motion of atoms increases, temperature increases. There seems to

be no upper limit of temperature but there is a definite limit at the other end of
the temperature scale. If we continually decrease the thermal motion of atoms
in a substance, the temperature will drop.

Absolute zero is the temperature at which no more energy can be extracted

from a substance.

At absolute zero, no further lowering of its temperature is possible. This

temperature is 273 degrees below zero on the Celsius scale. Absolute zero
corresponds to zero degrees on the Kelvin, or thermodynamic, scale and is
written 0 K (short for “zero Kelvin”).

Unlike the Celsius scale, there are no negative numbers on the thermodynamic scale.
Degrees on the Kelvin scale are the same size as those on the Celsius scale. Ice melts at
0°C, or 273 K, and water boils at 100°C, or 373 K.
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Some state variables

P versus T plots of the

experimental data obtained
from a constant-volume gas
thermometer using four
different gases at different (but
low) pressures.

PV
T  lim
p 0 nR
(for ideal gas)

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Some state variables

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Equation of state

Consider thermodynamic system described by state variables {Z1, Z2,…, Zn}

Subspace of equilibrium states: f(Z1, Z2,…, Zn) = 0  This is the equation of
state (EOS)
Ideal gas: {T, P, V}  thermodynamics EOS: pV = nRT

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Ideal gas law

• Experiments with a wide variety of gases revealed

that four variables were sufficient to fully describe
the state of a gas
• Pressure (P)
• Volume (V)
• Temperature (T)
• The amount of the gas in moles (n)

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Ideal gas law

Ideal gas law

PV=nRT

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Ideal gas law

• Combine these relationships into a single fundamental

equation of state - the ideal gas equation of state

PV nRT
J L atm
R  8.314 0.08206
K mole K mole

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Ideal gas law

• The pressure exerted by gas #1: P1 = n1 RT / V

• The pressure exerted by gas #2: P2= n2 RT / V
• The total pressure of the gases: pT = nT RT / V
nT represents the total number of moles of gas present in the
mixture.
P1 and P2 are the partial pressures of gas 1 and gas 2, respectively.
• PT = P1 + P2 = nT (RT/V)
• PT = P1 + P2 + P3 = Pi

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Ideal gas law

• Gaseous mixtures - gases exert the same pressure

as if they were alone and occupied the same
volume.
• The partial pressure of each gas, Pi, is related to the
total pressure by Pi = Xi PT
• Xj is the mole fraction of gas i.
• Xj= nj / nT

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Ideal gas

• An ideal gas is a gas that obeys totally the ideal gas

law over its entire P-V-T range
• Ideal gases – molecules have negligible
intermolecular attractive forces and they occupy a
negligible volume compared with the container
volume

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Ideal gas

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Ideal gas

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Real gas

PvT diagram for real gases

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Real gas

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Real gas

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Real gas

Several equations have been proposed to represent the P-v-T behavior of substances
accurately over a larger region with no limitations.

Critical isotherm
of a pure
substance has an
inflection point
at the critical
state.

This model includes two effects not considered in the

ideal-gas model: the intermolecular attraction forces and
the volume occupied by the molecules themselves. The
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accuracy of the van der Waals equation of state is often
inadequate.
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Real gas
critical point is defined as the point at which the saturated liquid and saturated vapor
states are identical.
At the critical point, only one phase exists. There is an inflection point in the constant-
temperature line (critical isotherm) on a PV diagram. This means that at the critical
point:

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Real gas

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Real gas

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Real gas

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Real gas

Compressibility factor Z A The farther away Z is from unity, the more the gas
factor that accounts for the deviates from ideal-gas behavior.
deviation of real gases from Gases behave as an ideal gas at low densities (i.e.,
ideal-gas behavior at a given low pressure, high temperature).
temperature and pressure. Question: What is the criteria for low pressure and
high temperature?
Answer: The pressure or temperature of a gas is
high or low relative to its critical temperature or
pressure.

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Real gas

All substances obey the same equation of state in terms of reduced variables

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Real gas

Reduced Reduced
pressure temperature

Pseudo-reduced specific volume Z can also be determined from a

knowledge of PR and vR.

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Comparison of Z factors for various gases.
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Real gas

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Real gas

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Real gas

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Real gas

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