THERMODYNAMICS

Most of the physical and chemical processes in the nature occur due to energy
changes. Energy is a state function of the system, defined as a property which
can be converted to work. Thermodynamics is one such study of energy and its
transformations. It is defined as a study of inter-relation of various forms of
energy systems (may be physical or chemical) under a set of conditions
constitutes the subject of thermodynamics. This study is of prime importance
as it is used to deduce and elucidate the following aspects of physical
chemistry such as:

1. Vant Hoff`s Law

2. Phase rule
3. Laws of chemical equilibrium

Applications of thermodynamics

The criteria of the feasibility or spontaneity of chemical reactions under

a given set of conditions are explained by the laws of thermodynamics.
The study also determines the extent until which
Reactions can proceed.

Limitations of the study

The laws of thermodynamics are applicable to substances of
macroscopic aggregation or bulk, but not to the individual atoms or
molecules of systems. The reason is due to the atoms being highly
unstable and studying the thermodynamics of such molecules become
immensely difficult.
The laws account for the feasibility of a reaction, however fails to predict
the rate of the reaction.

Important terminologies:
System
A portion of the universe which is chosen for thermodynamic study.
It consists of a definite amount of specific substances which is
surrounded by a well-defined boundary.
 Illustrations: Consider the case of a piece of ice. The existence of only ice is a
state function which depends on both pressures (P) and temperature (T).
Studying the thermodynamics of the ice becomes the system.

Surrounding

Part of the universe remaining outside the boundaries of a system which

can exchange both energy and matter. The system is separated from the
surrounding by a boundary. This can be a fixed, movable real or
imaginary.

Entropy

Is a quantitative term deciding the feasibility of a reaction. It refers to

the randomness or the disorderness of a system. It is denoted by S. The
total entropy is given by S(total) =S(system) +S(surrounding). If a process is
carried out in a thermodynamically reversible manner, so that dq is the
amount of heat absorbed by the system at constant temperature, then
the entropy change, ds, of the system id given by the expression,
ds= dq/dt

If S2 is the entropy of the final state and S1 is the entropy of the initial
state of a system under investigation, the increase in the entropy s, is
given by the equation,
s=S2-S1=dq/dt
Entropy is expressed in calories per degree or Joules per degree kelvin.
(JK-1)

Types of systems
Open system
A system which can exchange both energy and matter. A typical
example can be water present in an open container. The water here
represents the system. As the container is open, more water can be
added and hence the thermodynamics of such a system can be
monitored efficiently.
Fig 1 An exchange of matter and energy in an open system

Vapour
Heat
Water
 Closed system
A closed system is one in which no transfer of matter to and from the
surroundings is possible but energy can be exchanged across the
boundaries with the surroundings.

Fig 2 A closed systems in which there is exchange of energy with the

surroundings

No exchange of matter
with surroundings

Water

Heat

Thermally isolated system

A system which can exchange neither energy nor matter with its
surrounding is called an isolated system. A definite amount of water sealed or
enclosed in a container which is thermally insulated. The system does not
exchange heat or matter with the surrounding and retains the same state and
thermodynamic properties.

Fig 3 No exchange of energy and matter in an isolated system

Insulated closed
system
No exchange of
matter and energy

Surroundings

Thermodynamic properties of a system

 The characteristic physical properties such as pressure, temperature, volume,
mass, density, internal energy, enthalpy, etc, are known as thermodynamic
properties which defines the state of the system. Since the state of the system
changes with the change in any of the properties are called as state variables.
It follows that when a system changes from one state to another, there is
invariably a change in one or more of the thermodynamic properties.

Thermodynamic equilibrium of a state

The state of a system in which the macroscopic properties do not undergo any
change with time is said to be in thermodynamic equilibrium.

Example: Ice in a refrigerator, a substance in a vacuum flask.

Types of processes in thermodynamics

1. Isothermal process
A process is said to be isothermal if the temperature of the system
remains unaltered during each stage of the process.
2. Isobaric process
A process is said to be isobaric if the pressure of the system remains
unaltered during each step of the process.
3. Adiabatic process
A process is said to be adiabatic if no heat enters or leaves the system
during each step of the process.
4. Isochoric process
A process is said to be isochoric if there is no change in volume of the
system during each stage of the process.

First Law of thermodynamics

This law is a version of law of conservation of energy for
thermodynamic systems. The law states that the total energy of an
isolated system is constant and can be transformed from one form to
another but cannot be created or destroyed.

Example for the first law

When an engine burns fuel, it converts the energy in the fuels chemical
bonds into useful mechanical work and then to heat. Different fuels
 have different energy, but in any given gallon or litre of fuel, there is a
set amount of energy.
The conversion of energy principle defined by the first law says that
when all the fuels energy is released by burning the engines cylinder, it
doesnt disappear. The total quantity of energy stays same and is
accounted for. For every 100 units of fuel energy that is burned, 100
units of converted energy has to end up somewhere. It doesnt
disappear.

Applications of first law

In an open system
Can predict how much the pressure drop is across the nozzle or how
much energy is required by the pump to pump fluid.
amount of heat transfer in the heat exchanger
Amount of work produced by the turbine..

In a closed system

A piston cylinder arrangement

W

A cylinder has some gas in it. Assume there is no air leakage to the
surrounding. So it is a closed system. Assume gas is absorbing some heat Q,
also assume that the gas is able to push the piston upwards due to high
pressure of the gas. This enables the gas to perform work.

Therefore; E=Q-W de/dt=Q-W