Advanced Engineering

Thermodynamics
The Basics Concepts
Lecture 1
Fundamental of Engineering
Thermodynamics

 System – distinguished from its surroundings by a

specified boundary, either at rest or motion
 Open System – Transfer of mass across the boundary
 Close System – NO Transfer of mass across the boundary
Fundamental of Engineering
Thermodynamics

 Property – Characteristic of system to which numerical value can be assigned

at given time without knowledge of previous behaviour (history)
 State – Condition of system specified by properties
 Process – Transformation from one state to another
 Steady State – No property of system changes with time
Fundamental of Engineering
Thermodynamics

 Thermodynamic Cycle – a sequence of processes that begins and ends at the

same state.
 The change in the property is determined by two end states and independent of
particular way the change occurred
 Extensive State Properties – whose value does not depend on the amount of a
particular substance that is present i.e. Pressure and Temperature
 Intensive State Properties – whose values depends on the amount of substance
e.g volume, internal energy
Fundamental of Engineering
Thermodynamics

 Phase – throughout which all physical properties of a material are essentially

uniform.
 A pure substance can exist in more then one phase, but its chemical composition
must be same in each phase
 Equilibrium – balance maintained by not only equality of opposing forces but
also a balance of other influences
 Non-equilibrium states exhibits variations in intensive properties at a given time
 Quasi-equilibrium the transition from thermodynamics equilibrium is at most
infinitesimal.
Quasi-static process

 An equilibrium state represented by a set of properties (x1, y1)

 weight of the piston balances the upward force exerted by the gas
 the initial and final states can be located in a generalized 2 dimensional diagram

 Fig: 1.6 Fig: 1.7

 A quasi-static process is thus a succession of equilibrium states
 The character of such a process is that it is infinitely slow process
 A reversible state is a quasi-static process without any dissipation
Energy interactions

 In thermodynamics 2 (two) types of energy are considered

 Heat and Work
 Work converts to work only; final form of energy is work only.
 Heat to heat interactions always involve degradation.
 Work converted to heat is not useful, we call it as dissipation of energy.

 In thermodynamics basic interest is conversion of heat into work.

Laws of Thermodynamics

 Interactions of energy at system boundary is governed by certain laws

 Four basic laws in classical thermodynamics.
 TheZeroth law, first law, second law and third law of thermodynamics
 Law applied to irreversible thermodynamics developed by Onsagar in the year 1957,
termed as fourth law of thermodynamics.

Thermodynamic Laws Scientists/Researchers Year

Zeroth Law Fowler and Guggenheim 1939
First Law Joule, Mayer, Thompson and Colding 1845
Second Law Carnot 1824
Third Law Nernst 1907
Fourth Law Onsagar 1968

 The zeroth law and third law are more definitional in nature. The first and the
second laws are more pragmatic and as an engineer we use both these laws for
analysis.
Laws of Thermodynamics

 Zeroth law gives the definition of temperature

 Temperature is the only property which differentiates thermodynamics from other
sciences
 First law of thermodynamics
 first law of thermodynamics is that energy is conserved

 First Law gives a quantative measure of energy

 It can not distinguish the different types of energy
 It fails to indicate the direction of flow of energy
 It can not indicate whether the process is cyclic or not.
 First law applied to a process gives rise to a property (internal energy, U for a closed
system and enthalpy, h for a open system)
Laws of Thermodynamics

 First law efficiency indicates conversion of energy in a cycle as given by Eq.

(1.1)

 The net output can be work or heat depending upon the application.
 In case of a heat engine, the net output is in the form of work
 in case of a solar water heating system it can be the useful heat.
 The difference between the net output and input is the energy unused.
 It is always the need from the first law of the thermodynamics to reduce the
energy waste from the system
Laws of Thermodynamics

 The second law of thermodynamics

 the exergy, which is a consequence of the second law, is never conserved
 Unlike energy, exergy always decreases
 The net exergy output to the actual exergy input to the system is the second law
efficiency

 Exergy is a tool to identify the loss of energy

 Apart from the energy conservation, two important implications of second law
of thermodynamics
 Directional flow of energy
 Qualitative measurement of energy
Laws of Thermodynamics

 Directional flow of energy

 A spontaneous process occurs only in one direction. Reverse of these processes
never happen spontaneously.
 The spontaneous process is due to a finite driving potential called FORCE or CAUSE.
The outcome or result is called the FLUX, CURRENT or EFFECT

Sl No Force (Cause) Conjugate fluxes (Effect)

1 Temperature Gradient Heat Transfer

2 Concentration Gradient Mass Transfer

3 Electric Potential Gradient Flow of Electric Current

TRANSFER PROCESSES CAN NEVER SPONTANEOUSLY OCCUR FROM A LOWER TO A

HIGHER POTENTIAL. SECOND LAW OF THERMODYNAMICS PUTS LIMITATION ON
DIRECTION OF PROCESS OCCURANCE.
Laws of Thermodynamics

 Qualitative measurement of energy

 The second law distinguishes energy in two different forms
 (1) High grade energy and (2) Low grade energy.
 High grade energy is an orderly form of energy whereas low grade energy is in random
form. Some high and low grade energy forms are given in Table 1.6.

High Grade Energy Low Grade Energy

Electrical energy Thermal Energy from Fossil Fuel
Wind energy Nuclear Fission
Hydropower Nuclear Fusion
Kinetic energy of a water jet Waste Heat from Thermal Power Plant
Mechanical work Solar Thermal Energy
Tidal power Geothermal Energy

Quality of energy can be ascertained by applying the second law of

thermodynamics to a process or a system
Thermodynamic Properties

 Both the first and second law of thermodynamics while applied to processes
give rise to some thermodynamic properties
 First law of thermodynamics for a closed system give rise to a property called
internal energy U
 ∴ Q - W = ΔE
 Q2 + Q3 - Q1 = ΔE + (W2 + W3 - W1 - W4)

 The energy is an extensive property. The specific energy

(J/kg) is an intensive property.

 The cyclic integral of any thermodynamic property is zero (∫dE = 0)
Different Forms of Stored Energy

 Total energy stored in a system is represented by E. Basically there are two

models in which energy may be stored in a system
a. Macroscopic energy mode
b. Microscopic energy mode
 The macroscopic energy mode includes the macroscopic kinetic energy and
potential energy of a system i.e, mV2/2 and mgz
 The microscopic energy mode refers to the energy stored in the molecules
and atomic structure of the system, which is called the molecular internal
energy or simply internal energy U
 They can have translational kinetic energy, rotational kinetic energy,
vibrational energy, electronic energy, chemical energy and nuclear energy
Different Forms of Stored Energy

 If ε represents the energy of one molecule, then

 If N is the number of molecules in the system, then the total internal energy
is U = NꜪ
 For an ideal gas there are no intermolecular forces of attraction and
repulsion, and the internal energy depends only on temperature U = f(T)
 Other forms of energy which can also be possessed by a system are magnetic
energy, electrical energy and surface tension energy. In absence of these
forms, the total energy E of a system is given by E = (EK + EP) + U, where EK +
EP Macro energy and U = Micro energy
 In absence of motion and gravity, E = U
Relationship between the first and
second law of thermodynamics
 Consider a power plant converting a fraction of available energy A or W max to
useful work W

A thermodynamic cycle (a) sink at temperature T2 and (b) sink at ambient

condition T0
Relationship between the first and
second law of thermodynamics
 For the desired output of W,
Amin = W
A = Wmax
∴ I = Irreversibility = Wmax - W

where ηcarnot is the Carnot efficiency of an engine operating between two fixed
temperatures. Efficiency of any thermodynamic cycle cannot be more than the Carnot
cycle efficiency
Thermodynamics Processes

 Second law of thermodynamics enables us to divide all the processes into two
classes:
 Reversible or ideal process
A process is reversible if, after the process has been completed, means can be found to
restore the system and its elements of its and the surroundings to their respective initial
states

 Irreversible or natural process

Any process, which is not reversible, is irreversible. All natural (spontaneous) processes are
irreversible