Recapitulations: The Properties of Gases

• Ideal Gas vs Real Gases: Molecular Interactions

• Critical constants

• Compression factor, Z

• Real gases equations of state:

(a) Virial , nRT  nB n C 2

p= 1 + + 2 + ......
(b) van der Waals V 2 V V 
 an 
 p + 2 (V − nb ) = nRT
 V 
• The liquefaction of gases
 Thermodynamics
(from the Greek thermos meaning heat and dynamics meaning power)

Sadi Carnot (1796-1832) James Prescott Joule (1818-1889)

William Thomson (Lord Kelvin) (1824–1870)

Rudolf Clausius (1822 - 1888) Ludwig Boltzman (1844 - 1906)

 Outline

First law of thermodynamics: (lecture: 1)

• System and surroundings

• Work, heat and energy

• Work done in reversible and irreversible

processes
 Thermodynamics
Study of the effects of changes in temperature,
pressure, and volume on physical systems at the
macroscopic scale by analyzing the collective motion of
their particles using statistics.

It tells us about

•Heat output of a chemical reaction.

•Work output from a chemical reaction.
•Why a particular reaction reaches equilibrium?
•What is the equilibrium composition of a reaction?
 Thermodynamics
• Classical thermodynamics- independent of any model of
the microscopic structure of matter.

• Statistical Thermodynamics provides link between

microscopic structure and macroscopic thermodynamic
properties.
• System: That portion of the universe set apart for
detailed study and analysis.
• Surroundings: Rest of the universe, with which
the system can interact.
 Classification of Systems
• Open System – One that can
exchange matter as well as
energy with its surroundings.
• Closed System – One which
can exchange energy but not
matter with the
surroundings.
• Isolated System – One which
is completely unaffected by
the surroundings.
 Mechanical Equilibrium

A system is in mechanical equilibrium with its

surroundings if it is separated from them by a
movable wall and the external pressure is equal to
the pressure of the gas in the system.

A system is in mechanical equilibrium when the

sum of the forces, and torque, on each particle of
the system is zero.
 Properties
Temperature

This property of an object determines the
direction of flow of energy when it is in thermal
contact with another object.

Energy flows from higher to lower temperature.

In thermodynamics, temperature is a measure of

the tendency of an object or system to
spontaneously give up energy.
 Thermal Equilibrium

When two objects in thermal contact with each

other have the same temperature, although there is
still transfer of energy in both directions, there is
no net flow of energy between them.

Objects are in thermal equilibrium.

The objects will approach the same temperature,

and in the absence of loss to other objects, they will
then maintain a constant temperature.
 Properties
Measurement
Celsius scale and Kelvin of Temperature
scale

T (in Kelvin) = θ (in degree Celsius, oC) + 273.15

More sophisticated way of expressing the relation

between T and θ is as follows:
T/K = θ/oC + 273.15

A relation between pure numbers.

 Properties
Amount of substance:

The mass, m of a sample is a measure of the

quantity of matter it contains.

The SI unit of mass is the kilogram (kg).

In chemistry, convenient way of expressing amount

is in terms of mole.

×1023
1 mol of any substance contains 6.02214199×
particles.
 Extensive and Intensive Properties

Extensive Property: A property that depends

on the amount of the substance in the sample.
e.g., mass, volume

Intensive property: A property that is independent

of the amount of the substance in the sample; e.g.,
pressure, temperature, molar volume.

Extensive properties are additive but intensive

properties are not.
 Extensive and Intensive Properties
Some intensive properties are ratios of two
extensive properties, e.g., density of a substance.
It is ratio of two extensive properties mass and
volume.

Specific property:
Given any extensive property, one may divide it by
the mass to obtain an intensive property called a
specific property.
For example, Specific Volume = Volume per Unit
Mass.
 Work, Heat and Energy
A system does work when it causes motion against
an opposing force.
From mechanics, Work done, δw = Fdx
The total work done when the system moves an
object from xi to xf against an opposing force F, is
the sum of infinitesimal contributions along the
path xf
w = ∫ Fdx
xi

If F is independent of position, then

w = F(xf – xi)
 Work, Heat and Energy
•Work done against gravitational force mg in
raising an object of mass m on the surface of earth
by a distance h = (xf – xi) is therefore
w = mgh
Note: SI unit of work, 1Joule = 1 kgm2s-2
Work of expansion: − PexdV
Work of compression: PexdV
Where Pex is external pressure and dV is volume
swept out in expansion and swept in in
compression.
 Work, Heat and Energy
Energy:
Energy is capacity of a system to do work.

When work is done on a system (for instance, by

compressing a gas), its energy is increased.
Therefore, its capacity to do work increases.

When the system does work (for example by

moving out a piston), its energy is reduced because
it can do less work.
Total energy = Kinetic energy (EK) + Potential
energy (EP).
 Work, Heat and Energy
Exchange of energy between a closed system and its
surroundings can occur not only by doing WORK
but also by the process called HEAT TRANSFER.
When the energy of a system changes as a result of
a temperature difference between it and its
surroundings we say that energy has been
transferred as heat.
Therefore, a hot object can do more work than the
same object when it is cool. A hot object has a
higher energy than the same cool object.
SI unit of energy is joule(J), 1J = 1kgm2s-2
 Work, Heat and Energy
Exothermic process: A process that releases energy as
heat. All combustion reactions are exothermic.
Endothermic process: A process that absorbs energy as
heat, e.g., vaporization of water.
• A wall that permits passage
of energy as heat is called
diathermic

• A wall that does not permit

the passage of energy as heat
although there is a
temperature difference across
the wall is called adiabatic.
 Work, Heat and Energy
An exothermic process in an adiabatic container
results in a rise of temperature of the system.

An endothermic process in an adiabatic container

results in a lowering of temperature of the system.
An exothermic process taking place in a diathermic
container under isothermal conditions results in a
release of energy as heat into surroundings.
An endothermic process in a diathermic container
under same conditions results in flow of energy into
the system as heat.
 Work, Heat and Energy
Example of different ways of transferring energy

Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g)

 Work, Heat and Energy
Molecular Nature of Work and Heat
 Work, Heat and Energy
Measurement of Work and sign convention
Work done against gravity in raising an object of mass m
by a distance h = mgh.
•SI unit of work 1Joule = 1 kgm2s-2
When energy enters the system as work and heat,
then work, w > 0 and heat, q > 0.
But when energy leaves the the system as work and heat,
then work, w < 0 and heat, q < 0.
 Work of Expansion
The work done when a system expands against an
opposing pressure.

Work δw = -(PexA)h = -Pex ∆V

Total work of expansion against a constant external

pressure, Pex when a change in volume is ∆V is
w = −Pex ∆V
Free Expansion: Expansion against zero external
pressure. Work = 0
 Work of Compression

The work done on a system when it is compressed

due to external pressure.
Work, δw = − (PexA)h = − PexdV
Where Pex is the external pressure.
Total work of compression, w = −Pex ∆V

Note: Sign of work now positive, since dV < 0

 Maximum Work of Expansion or
Compression
Reversible work:
Reversible process: A reversible process in
thermodynamics is a process that can be reversed
by an infinitesimal modification of a variable.
When a system is in equilibrium with its
surroundings then an infinitesimal change in the
conditions in opposite directions results in opposite
changes in its state.
 Maximum Work of Expansion or
Compression
Maximum expansion work will be done when the
external pressure will be only infinitesimally less
than the pressure of the gas in the system.
When the system is in mechanical equilibrium with
its surroundings at all stages of the expansion, then
maximum expansion work will be done.
Therefore, maximum expansion work will be
achieved in a reversible process.

δw = -pdV
Total work when the system expands from Vi to Vf
under isothermal reversible condition is,

W = -nRTln(Vf/Vi) , Vf being greater than Vi

< 0, work done by the system.
W<
Reversible Work:
Maximum work of compression,
W = -nRTln(Vf/Vi), Vi being greater than Vf
W > 0, work is done on the system.
Reversible isothermal expansion work of a perfect gas,
W = -nRTln(Vf/Vi) and
Reversible isothermal compression work of a perfect
gas, W = nRTln(Vi/Vf)
 Maximum Work of Expansion or
Compression
Reversible Work:

For a given change of

volume and fixed
amount of gas the work
of reversible isothermal
expansion of a perfect
gas is greater the higher
the temperature.
For a gas to expand reversibly, the external
pressure must be adjusted to match the internal
pressure at each stage of the expansion.
Expansion Against Constant Pressure
Irreversible work:
Irreversible Process:
If the external pressure differs measurably from
the internal pressure then infinitesimal change in
either pressure will not reverse the process.

Therefore, we can say that the system is not in

equilibrium with the surroundings and if it is
expansion of a gas, then the expansion is said to be
thermodynamically irreversible.
Expansion Against Constant Pressure
Irreversible work:
If the external pressure is measurably smaller than
internal pressure then the expansion of gas will be
essentially against a constant external pressure Pex

For infinitesimal volume change dV, work done by

system, dW = - Pex dV

Therefore, total work done in the expansion from

Vi to Vf is W = - Pex(Vf - Vi) = - Pex∆V
Reversible work is maximum work and greater than
irreversible work for a given volume change

Vi Vf Pi
P P
Area = P=nRT/V
Pex∆V Pf
Pex

V V
Vi Vf Vi Vf
Reversible work done.
Superimposed rectangular
Irreversible work done area is work done in
irreversible process.