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Engineering Thermodynamics

Chemical equilibrium occurs when the chemical composition of a system no longer changes over time, meaning no chemical reactions are occurring. A quasi-static process involves infinitesimal changes from equilibrium, proceeding through a continuous succession of equilibrium states. A reversible process can be executed such that both the system and surroundings can be restored to their initial states without changes to the universe. Irreversible processes cannot be fully reversed without permanently altering the surroundings, often due to dissipative effects like friction or resistive losses. The first law of thermodynamics states that the sum of all work transfers equals the sum of all heat transfers during any thermodynamic process or cycle involving a closed system. The second law introduces the concepts of heat reservoirs and identifies limitations of

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92 views11 pages

Engineering Thermodynamics

Chemical equilibrium occurs when the chemical composition of a system no longer changes over time, meaning no chemical reactions are occurring. A quasi-static process involves infinitesimal changes from equilibrium, proceeding through a continuous succession of equilibrium states. A reversible process can be executed such that both the system and surroundings can be restored to their initial states without changes to the universe. Irreversible processes cannot be fully reversed without permanently altering the surroundings, often due to dissipative effects like friction or resistive losses. The first law of thermodynamics states that the sum of all work transfers equals the sum of all heat transfers during any thermodynamic process or cycle involving a closed system. The second law introduces the concepts of heat reservoirs and identifies limitations of

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Shiba Narayan Sahu
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Chemical Equilibrium(Equality of chemical potential):

A system is in chemical equilibrium when its chemical composition does not change with
time, that is no chemical reaction occurs .
It is related to chemical potential.
QUASI-STATIC PROCESS

A quasi-static process is one in which the deviation from thermodynamic equilibrium is


infinitesimal.
Characteristics:
Infinite slowness is the characteristic feature of this process.
A quasi-static process is thus a succession of equilibrium states.
It can be represented as a continuous line on the property diagram.
It is also known as a reversible process.
REVERSIBLE PROCESS
Reversible process is one which is performed in such a way that at the end of the process both
the system and surrounding may be restored to their initial state without producing any changes
in rest of the Universe.
Reasons for studying Reversible Process:
1.They are easy to analyze.

2. They served as an idealized process to which actual process can be compared.


3.They are taken for consideration because work producing devices such as steam turbine,
automobile engines etc delivers the max. work and work consuming devices like compressors,
pumps etc consumes the least work.
Characteristics of Reversible Process
A Reversible process is carried out infinitely slowly with an infinitesimal gradient so that
every state pass through by the system is in equilibrium.
It is possible to execute the process in either of the direction.
No dissipative effect such as friction, loss in a resistor, etc are present.
Heat and work interactions of the system and the surroundings in the reverse process are equal
and opposite in direction to the same in the forward process.
Examples:
1. Frictionless isothermal expansion or compression of a fluid.
2. Frictionless adiabatic expansion or compression of a fluid.
3. Elastic stretching of a solid.
4. Electric current with zero resistance.
IRREVERSIBLE PROCESS
An irreversible process is one that is carried out in such a way that the system and surrounding
can not be exactly restored to their respective initial state at the end of the reverse process, that a
net change occurs in the Universe.
Note: In an irreversible the surrounding would always be affected by loss of work and gain of
low temperature heat, which can be considered as waste heat for the surrounding.
Causes of an Irreversibility:
The irreversibility of a process may be due to either one or both of the following.
(i) Lack of Equilibrium.
(ii) Involvement of Dissipative effects.

Lack of Equilibrium(Mechanical,Thermal,Chemical)
The lack of equilibrium between the system and the surroundings or between the two systems
causes a spontaneous change which makes the process irreversible.
Examples:
1. Heat transfer through a finite temperature difference.
2. Compression or Expansion through a finite pressure difference between the system and
the surroundings.
3. Free expansion or Unrestrained expansion.
4. Mixing of substances.
Dissipative Effects:
Dissipation results in the transformation of work into molecular energy of the system.
Examples:
1. Friction.
2. Flow of electricity through a resistor.
3. Paddle wheel work transfer. etc
Characteristics of an Irreversible Process:
1. It can be carried out in one direction only.
2. It occurs at a finite rate.
3. During an irreversible process, the system is not in equilibrium.
An irreversible process cannot be reversed without causing permanent changes in the
surroundings.

Heat & Work Transfer


Thermodynamic Work: Work is said to be done by a system if the sole effect on things
external to the system can be reduced to the raising of a weight.
Displacement (or) pdV Work:

Expression for pdV Work:

Sign Convention for work transfer:


Work done by the system is positive and Work done on the system is negative.

Work done during various Quasi-static Processes:


Constant Pressure Proces:

Constant Volume Process:

Constant Temperature Process:

Polytropic Process

, where n is a constant

Heat Transfer: Energy transfer by virtue of temperature difference is called Heat Transfer. Heat
Transfer is also a boundary phenomenon.
Specific Heat: It is the amount of heat required to raise the temperature of unit mass of a
substance by unit degree.
For Solids and Liquids
cp = cv = c
For Gases
cp specific heat capacity at constant pressure
cv specific heat capacity at constant volume
Latent Heat: It is the amount of heat transferred to cause a phase change.

FIRST LAW OF THERMODYNAMICS


This is based on Law of Conservation of Energy.
This is also called as First Principle.
For a closed system, undergoing a cycle
Sum of all Work transfers = Sum of all Heat Transfers
(W1+W2+W3

(W)

(Q1 +Q2+Q3
(Q)

For a closed system,undergoing a Process


Whenever heat is absorbed by a system it increases its internal energy and does some work.
Q= E+W
Where

heat absorbed by the system

Work output from the system

Change in Stored Energy of the system

Show that Energy is a property of the system

For path A,
(1)

For path B,
(2)
For path B,
(3)
For Cycle 1-A-2-B-1,
(4)

(A)
For Cycle 1-A-2-C-1,

(C)
Comparing A and C

Enthalpy:
It is the energy content of the flowing fluid.
It is defined by the summation of internal energy and flow work.
H = U + PV
Note: For an ideal gas h = u + Pv.
= u + RT
So, h = f(T)
Define Cv with the help internal energy and Temperature:
The amount of heat required to raise the temperature of unit mass of a substance by 1o C in a
reversible constant volume process.

Cv is also defined as the change of internal energy of the substance per unit change in
temperature at constant volume.
Define Cp with the help enthalpy and Temperature:
The amount of heat required to raise the temperature of unit mass of a substance by 1o C in a
reversible constant pressure process.

C p is also defined as the change of internal energy of the substance per unit change in

temperature at constant pressure.


Application of First law to different Thermodynamic process:
Process

Index=n

Rev. Const.Vol.

W=
W=0

=
Rev.Const.pressure n=0
=
Rev. Isothermal

n=1

Rev.Adiabatic

n=

Rev.Polytropic

Q=0

P-V-T Relation

MODULE-2
SECOND LAW OF THERMODYNAMICS
State the limitations of first law of thermodynamics?
1. First Law places no restriction on the direction of a process.
2. It does not ensure whether the process is feasible or not.
3. This law does not differentiate heat and work. It is concerned with the quantity of energy and
the transformation of energy from one form to another with no regard to its quality.
Aspects of the second law
1. To identify the direction of process.
2. Establishing conditions for equilibrium.
3. It also asserts that energy has quality as well as quantity.
3. It is also used in determining the theoretical limits for the performance of heat engines and
refrigerators.
4. Defining a temperature scale independent of the properties of any thermometric substance.
Thermal Energy Reservoir (TER): It is a hypothetical body with a relatively large thermal
energy capacity that can supply or absorb finite amount of heat without undergoing any change
in temperature. Examples: Oceans, rivers, atmospheric air etc.
TER that supplies energy in the form of heat is called a source
TER that absorbs energy in the form of heat is called a sink
Heat Engines: Heat engine is a cyclic device, used to convert heat to work. Heat engine can be
characterized by the following points.
1. They receive heat from a high temperature source (solar energy, oil-furnace etc.)
2. They convert part of this heat to work (usually in the form of a rotating shaft)
3. They reject the remaining waste heat to a low temperature sink (the atmosphere, rivers, etc)
4.They opertate on a cycle.

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