Introduction to thermodynamics

Introduction

In this topic, we discuss the historical background of thermodynamics, define

thermodynamics and thermodynamic systems. We introduce some of the terminologies
used in thermodynamics. Finally we discus and define thermodynamic equilibrium,
homogeneous and heterogeneous systems.

Objectives

By the end of this topic, learners should be able to:

 Define thermodynamics
 List some of the applications of thermodynamics
 Define a thermodynamic system and state the different types of thermodynamic
systems
 Differentiate between control volume and control mass
 State the difference between macroscopic and microscopic thermodynamic
approaches
 Give examples of state variables
 Differentiate between intensive and extensive variables
 Define thermodynamic equilibrium
 Discuss the requirements for a system to be in thermodynamic equilibrium
 Differentiate between quasi-static and non quasi-static processes
 Explain what is meant by homogenous and heterogenous systems

Thermodynamics

The science of thermodynamics had its start in the early part of the nineteenth century,
primarily as a result of attempts to improve on the efficiency of the steam engines,
devices in which there is input in form of heat and output in form of mechanical work.
Thus as the name implies, thermodynamics was concerned with both thermal and

1
mechanical/dynamical concepts. As the subject developed and its basic laws were fully
understood, its scope became broader.

We can define thermodynamics as the study of energy and its surroundings. There are
basically two forms of energy to be considered namely: - Heat and work. It is concerned
with only large scale (macroscopic) properties of matter and it makes no idea
(hypothesis) suitable to explain the facts about small scale (microscopic) structure of
matter. The Design and Analysis of many engineering systems requires thermodynamic
principles. Some of the applications of thermodynamics include:

 All types of vehicles that we use, cars, motorcycles, trucks, ships, aeroplanes,
and many other types work on basis of second law of thermodynamics and
Carnot cycle. They may be using petrol engine or diesel engine, but the law
remains the same
 All the refrigerators, deep freezers, industrial refrigeration systems, all types of
air conditioning systems, heat pumps, etc work on the basis second law of
thermodynamics
 Propulsion systems for rockets, missiles ….etc use thermodynamic principles.
 All types of air and gas compressors, blowers, fans run on various
thermodynamic cycles
 One of the important fields of thermodynamics is heat transfer, which relates
transfer of heat between two media. The three modes of heat transfer are
conduction, convection and radiation. The concept of heat transfer is used in
wide range of devices like heat exchangers, condensers, radiators, coolers,
heaters…etc
 Thermodynamics also finds applications in various types of power plants like
thermal power plants, nuclear power plants, hydro electric power plants, and
power plants based on renewable energies like solar, wind, geothermal….etc

2
Thermodynamic system:

It is defined as a definite quantity of matter or a region in space around which we can

draw a boundary.

Surroundings: Everything external to the system. Universe: a combination of a system

and its surroundings

System boundary: An interface separating a system and the surrounding.

There are two distinct ways of interaction between system and surroundings

 Mass interaction
 Energy interaction (like heat, work, etc.)

The system boundary sometimes permits either both types of interaction or only one
type of interaction or no interaction. Based on the interaction scenario between the
system and surroundings, thermodynamic systems can be classified into three
categories.

 Open system
 Closed system
 Isolated system

3
Open system: refers to thermodynamic systems where both the mass interaction and
energy interaction occur between the system and its surroundings. Examples are boiler,
Nuclear reactor, Combustion chamber, Turbine, Condenser, Pump, Heat exchanger, etc.

Closed system: Refers to thermodynamic systems where only energy interaction occurs
between the system and its surroundings. Thus, no mass interaction occurs between a
closed system and its surroundings. Examples of closed system: Refrigerant or working
fluid of refrigerator unit, Coolant of nuclear PWR or PHWR, Hot water kept inside a
PETE bottle.
Isolated system: Refers to thermodynamic systems where neither mass interaction nor
energy interaction occurs between the system and its surroundings. Examples of
isolated system: A perfect isolated system does not exist as energy interaction in the
form of heat radiation will always occur so long as there exists temperature difference
between system and surroundings. Practically, the matter inside a flask having inbuilt
radiation shields can be considered as isolated system.

4
Control volume: fixed volume over which mass can pass in and out of its boundary. A
control volume is bounded by a control surface.

• The surface may be open or closed to mass flows and it may have flows from energy
in terms of heat transfer and work across it.

• In the case of a control surface that is closed to the mass flow, so that no mass can
enter or escape the control volume, it is called a control mass containing same amount
of matter at all times.

Process

Change of state is called a process

Process path

The infinite states through which the system passes while going from initial state to
final state is called process path.

Macroscopic thermodynamics

In macroscopic thermodynamics, the average molecular behavior is taken into

consideration. The state of a system is specified by the values of certain experimentally
measurable quantities called state variables e.g temperature, pressure, volume.

Extensive variables: A variable which is dependent on mass e.g. Volume, mass, Kinetic
energy etc

Intensive variables: A variable which is independent of mass e.g. specific heat,

temperature, pressure.

Microscopic thermodynamics

In this case, individual molecular behavior is taken into consideration.

5
Thermodynamic equilibrium

Thermodynamic equilibrium is the state of a system in which there is no net flow.

A system in thermodynamic equilibrium is one whose thermodynamic properties do

not change when it is isolated from its surroundings. Even when the properties are
disturbed, the system will always tend towards thermodynamic equilibrium

The following types of equilibrium exist in a system in thermodynamic equilibrium.

 Mechanical equilibrium

 Thermal equilibrium

 Chemical equilibrium

 Phase equilibrium

Mechanical Equilibrium

A thermodynamic system is said to be in mechanical equilibrium when there is no

unbalanced force within the system and also between the system and its surroundings.
Whenever an unbalanced force exists, a state occurs that tries to restore equilibrium.

Chemical equilibrium

A system is in chemical equilibrium if there is no chemical reaction taking place in any

part of the system.

Thermal equilibrium

When there is no temperature difference between any two points in a system (uniform
temperature), then the system is said to be in thermal equilibrium.

Phase equilibrium

Mass of each phase should remain constant with time.

6
In any system once any of the above equilibrium is absent, then the system is said to be
in a non equilibrium state.

When a system undergoes a change of state in a non-equilibrium condition, it is

impossible to describe the thermodynamic properties which represent the system as a
whole.

Thus thermodynamic property is used only for thermodynamic equilibrium states and
only used as coordinates to describe a system.

Quasi –Static and non-quasi static process

Quasi –Static process is the kind of process that occurs infinitesimally slowly so that at
each instant the system remains in thermodynamic equilibrium. It is represented by
joined lines on property diagram. Quasi-static processes are done slowly enough that
the system remains in thermodynamic equilibrium at each instant despite the fact that
the system changes over time. For example imagine heating 1kg of water from a
temperature of to at constant pressure of 1 atmosphere. To heat the water
very slowly we may imagine placing the container with water in a large bath which can
be slowly heated such that the temperature of the bath can rise infinitesimally slowly
from to . If we put 1kg of water at directly into a bath at , the
temperature of water will rise rapidly to in a non-quasi-static way. Non quasi
static process is represented by dashed lines on property diagram as shown in the
example below.

7
Other kinds of processes include:-

 Reversible process: if the process happens slow enough to be reversed

 Irreversible process: if the process cannot be reversed (like most of the processes)
 Isobaric process: constant pressure process.
 Isochoric process: constant volume process.
 Isothermal process: constant temperature process.
 Isentropic process: constant enthalpy process.
 Adiabatic process: no heat enters or leaves the system
 Cyclic process: where initial state is equal to the final state

Cycle: A thermodynamic cycle is defined as a combination of a number of processes

(atleast two) that a system undergoes through, having state changes in such way that it
attains its initial state.

Phase, Homogeneous and heterogeneous system

Phase: A quantity of matter is said to be in a single phase if the has a uniform physical
and chemical composition throughout. Three phases of a substance include solid, liquid
and gas.

Homogenous system

8
A system in single phase (solid, liquid or gas) is said to be a homogenous system. A
homogenous system has uniform physical structures and chemical composition.

Heterogeneous system

This refers to a system in more than one phase. A heterogeneous system may have a
combination of phases for example a mixture of solid, liquid and vapour phase.