Thermodynamics

? What is thermodynamics
 Thermodynamics is that branch of science that
deals with the quantitative relationship
between heat and other forms of energy.

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Some basic terms of thermodynamics
 System :- a specified part of
the universe that is under
observation.
 Surroundings:- the part other
than the system is known as the
surroundings.

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 Types of systems
 Open system :- the system that can
exchange matter as well as energy
with the surroundings.
 Closed system:- the system which
cannot exchange matter but can
exchange energy with the
surroundings.
 Isolated system:- the system which
cannot exchange matter as well as
energy is called an isolated system.

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Macroscopic and microscopic properties
 Macroscopic properties are those
properties which arise from the
bulk behaviour of matter. Eg:-
temperature , viscosity.
 Microscopic properties are those
properties which arise from the
microscopic particles of the
system .Eg:- intermolecular
forces.
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 Intensive and extensive properties
 Intensive properties are those
properties whose value is
independent upon the amount
of substance present in the
system . Eg:- temperature.

 Extensive properties are those Intensive properties

properties whose value does
depends upon the amount of
substance present in the
system.

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 State of the system
 The condition of existence of a system when
the macroscopic properties have definite value
is called the state of the system.

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 State Functions
A state function depends only on the present state of the system , not on the path
by which the system arrived at that state.

.However, q and w are not state functions •

.Other state functions are P, V and T •
 State variables or state functions
 A thermodynamic property
whose value depends on the
initial and final states of the
system and is independent of
the manner by which the
change is bought about.

 The process which brings

changes in the system is called
a thermodynamic process.

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 Internal energy
 The chemical nature of the
substance depends about the energy
which it possesses and also
depends upon the state of its
existence which is known as the
internal energy.
 It also depends upon the kinetic
energy of the particles in the
system.
 It is an extensive property.

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 Enthalpy
 The sum of the internal
energy and the sum of the
pressure volume work is
known as the enthalpy of the
system.
 Enthalpy is also an extensive
property.

 Enthalpy is denoted by “H”.

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 Reversible and irreversible process
 A reversible process is a process when it
is carried out slowly so that the system
and the surroundings are always at
equilibrium then the process is termed as
a reversible process.

 An irreversible process is a process which

takes place rapidly in the system such that
the system and the surroundings are not at
equilibrium.

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 The Zeroth Law of Thermodynamics
If object A is in thermal
equilibrium with object C,
and object B is separately
in thermal equilibrium with
object C, then objects A
and B will be in thermal
equilibrium if they are
.placed in thermal contact
 The First Law of Thermodynamics
The first law of thermodynamics is a statement of the conservation of
.energy
If a system’s volume is constant, and heat is added, its internal energy
.increases
 The First Law of Thermodynamics
If a system does work on the external world, and
.no heat is added, its internal energy decreases
 The First Law of Thermodynamics
Combining these gives the first law of thermodynamics. The change
in a system’s internal energy is related to the heat Q and the work W
:as follows
 The First Law of Thermodynamics
The internal energy of the system depends only on its temperature.
The work done and the heat added, however, depend on the details of
.the process involved
 Thermal Processes
This is an idealized reversible process. The gas is
compressed; the temperature is constant, so heat leaves
the gas. As the gas expands, it draws heat from the
reservoir, returning the gas and the reservoir to their
.initial states. The piston is assumed frictionless
 Thermal Processes
:Work done by an expanding gas, constant pressure
 Thermal Processes
If the volume stays constant, nothing moves and
.no work is done
 Thermal Processes
If the temperature is constant, the
pressure varies inversely with the
.volume
 Thermal Processes
:The work done is the area under the curve
--
 Thermal Processes
An adiabatic process is one in which no heat flows
into or out of the system. The adiabatic P-V curve is
similar to the isothermal one, but is steeper. One way
to ensure that a process is adiabatic is to insulate the
.system
 Thermal Processes

Another way to ensure

that a process is
effectively adiabatic is
to have the volume
change occur very
quickly. In this case,
heat has no time to
flow in or out of the
.system
Energy as Work (w) of Gas Expansion
Work = - (Force
x distance)

w = - (F x h)

w = - (P x A x h)
There fore w = - P V
)at constant P(

w = - nRT
)at constant V(
Work Gas Expansion
 Exchange of Heat (H)
by chemical systems
When heat is released by the •
q
H - system to the surroundings, the
.process is exothermic

When heat is absorbed by •

the system from the
q
H +
surroundings, the process is
.endothermic
 Enthalpies of Reaction (H)
The change in enthalpy, H, :Reactants
is the enthalpy of the
products minus the enthalpy
of the reactants:

H = Hproducts − Hreactants

This quantity, H, is called the enthalpy of

.reaction, or the heat of reaction
Products