Thermodynamic System

 A thermodynamic system is a volume in

space containing a quantity of matter that is
being studied for thermodynamic analysis.

 The system is bounded by an arbitrary surface called the boundary.

 It separates the system from the surroundings.
 The boundary may be real or imaginary, may be at rest or in
motion, and may change its size and shape.
 Mathematically speaking, the boundary has zero thickness, and
thus it can neither contain any mass nor occupy any volume in
space.
 The mass or region outside the system is called the surroundings or
the environment. The surrounding interacts in some fashion with the
system and hence has a detectable influence on the system.
Classification of System
Basically, there are three types of systems:
 open system
 closed system and
 isolated system
 Closed System

 A closed system (also known as a control mass) consists of a fixed

amount of mass, and no mass can cross its boundary. That is, no mass can
enter or leave a closed system. Examp: a piston-cylinder assembly filled
with gas.
 But energy, in the form of heat or work, can cross the boundary;
the matter may also change in chemical composition within the boundaries.
 The volume of a closed system does need to be fixed.
 Open System

 An open system, or a control volume, is a properly selected region in space

for which both mass and energy (heat and work) may cross the boundary.
Examp: Flow through nozzle, compressor, turbine.
 The boundaries of a control volume are called a control surface.
** In an engineering analysis, the system under study must be defined carefully. In most cases, the system
investigated is quite simple and obvious, and defining the system may seem like a tedious and unnecessary
task. In other cases, however, the system under study may be rather involved, and a proper choice of the
system may greatly simplify the analysis.
Isolated System
 An isolated system is one that is not influenced in any way by the
surroundings. This means that no mass, heat, or work cross the
boundary of the system.
 An Isolated system is a special case of closed system that does not
interact in any way with its surroundings.

Figure: Three types of thermodynamic System

Describing Systems and Their Behavior

Thermodynamic systems can be studied by the two approaches :

 Microscopic approach: statistically averaging the behavior of the
individual particles which make up the substance.
 Macroscopic approach (sometimes called Classical approach): large
scale behavior of a substance .
State and Property

 The condition of a system at any instant of time is called its state.

State at a given instant is determined by the properties of the system.
 At a given state, all the properties of a system have fixed values. If
the value of even one property changes, the state will change to a
different one.
Examp: Different phase of a given mass of water.
 A thermodynamic property is any characteristic of a system by which
its physical condition may be described. Its numerical value depends only
on the (local) thermodynamic equilibrium state of the system and is
independent of the path (that is, the prior history how that state was
attained).
Examp:
Some familiar properties: pressure P, temperature T, volume V, mass m.
less familiar ones : viscosity, modulus of elasticity, electric resistivity.

** The state of a system frequently may be completely identified from a

knowledge of only a few of its properties. The values of all remaining
properties can be determined from the values of the few that are used to
specify the state.
The ideal gas formula, pv = RT, is an example of such an equation of state
for a simple system.
Intensive property

Intensive properties are those that are independent of the extent or

mass of a system,
Example: Temperature T, pressure P, density ρ, velocity v, chemical
concentration etc.
 If a single phase system is divided arbitrarily into n parts, then the
value of a given intensive property will be the same for each of the n
subsystems. Thus intensive properties have the same value throughout a
system in equilibrium.
 If the system is not in equilibrium, the property vary from place to
place within the system at any moment [may be functions of both
position & time].
Extensive Property
Extensive properties are those whose values depend on the size or extent
of the homogeneous system..
Example: Total mass m, total volume V, total momentum, Energy E
and the quantity of electric charge etc.
 May change with time.
 A property is extensive if its value for the whole system is the sum of
its values for the various subsystems or parts. If a system is divided into
n(possibly unequal) parts, then the extensive property Y for the whole
system is
Ysys = ∑ i = 1 to n Yi
** Generally, uppercase letters are used to denote extensive properties
(with mass m being a major exception), and lowercase letters are used for
intensive properties (with pressure P and temperature T being the
obvious exceptions).
Specific Property
Extensive properties per unit mass or
mole are called specific properties.

Example: specific volume (v = V/m)

and specific total energy (e = E/m).
Process and Cycle

 Any change or transformation that a system undergoes from one

equilibrium state to another is called a Process. Or, A thermodynamic
process is the succession of thermodynamic states that a system passes
through as it goes from an initial state to a final state.
 A system subjected to a thermodynamic process normally experiences
a change in its thermodynamic state.
 A system passes through a completely specified path from an initial
state to a final state is called a process.
 The series of states through which a system passes during a process is
called the path of the process.
 Figure: Three process paths that change the Figure: A process between states 1 and 2
state of the system from A to B. and the process path.

 Process for which a particular property remains constant is designated

by the prefix iso- is often used to designate a process.
 Figure: A thermodynamic cycle

A system is said to have undergone a cycle if it returns to its initial

state at the end of the process through a series of state changes.
That is, for a cycle the initial and final states are identical. The change
in the value of any property for a cyclic process is zero.
Equilibrium
 Properties are truly defined when a system is in equilibrium.
 The word equilibrium implies a state of balance. In an equilibrium
state there are no unbalanced potentials (or driving forces) within
the system.
 A system in equilibrium experiences no changes with time when it is
isolated from its surroundings. Hence a system in equilibrium cannot
change in state without an interaction with its surroundings.
Classification of Equilibrium
There are many types of equilibrium, and a system is not in thermodynamic
equilibrium unless the conditions of all the relevant types of equilibrium are
satisfied.
 Thermal equilibrium if the temperature is the same throughout the
entire system. That is, the system involves no temperature differential,
which is the driving force for heat flow.

Figure: A closed system reaching thermal equilibrium.

 Mechanical equilibrium is related to pressure, and a system is in
mechanical equilibrium if there is no change in pressure or force at
any point of the system with time. (the study of mechanical
equilibrium is called statics).

 Phase equilibrium A phase equilibrium exists within a system when no

phase transformations (such as vaporization or melting) occur within
the system.

 Chemical equilibrium A system is said to be in chemical equilibrium

when no chemical reactions or no change in chemical composition
occur within the system. Phase equilibrium is also chemical equilibrium.

Since the subject matter of thermodynamics contains all these types of

phenomena, we lump all these definitions together to define
thermodynamic equilibrium.
Zero’th Law of Thermodynamics
It states that if two bodies are in thermal equilibrium with a third body,
they are also in thermal equilibrium with each other.

Consider three thermodynamic systems, A, B, and C. If system B is in

thermal equilibrium with (i.e., is the same temperature as) system C and
system B is in thermal equilibrium with system A, then system A is in
thermal equilibrium with system C.
 Figure: The zeroth law of thermodynamics
applied to a mercury in a glass
thermometer.

The zeroth law tells us that if the glass is at the same temperature as (i.e., is
in thermal equilibrium with) the surrounding fluid, and if the mercury is at
the same temperature as the glass, then the mercury is at the same
temperature as the surrounding fluid. Thus, the thermometer can be
graduated to show the mercury temperature, and this temperature is
automatically (via the zeroth law) equal to the temperature of its
surroundings.
Pressure
It is the average rate of change of momentum due to all the colliding
molecules on a unit area. Pressure is defined as a normal force exerted by
a fluid per unit area.
 When dealing with liquids and gases, it is ordinarily spoken of
pressure; for solids it is known as of stresses.
 The pressure in a fluid at rest at a given point is the same in all
directions.
 The actual pressure at a given position is called the absolute pressure,
and it is measured relative to absolute vacuum (i.e., absolute zero
pressure).
 Most pressure measuring devices, however, are calibrated to read
zero in the atmospheric, and so they indicate the difference between the
absolute pressure and the local atmospheric pressure.
 This difference is called the gage pressure. Pressures below atmospheric
pressure are called vacuum pressures.

+ ; for Pgage above the atmospheric pressure

- ; for Pgage below the atmospheric prresure
Temperature
 The temperature is a thermal state of a body which distinguishes a
hot body from a cold body.
 The temperature of a body is proportional to the stored molecular
energy i.e. the average molecular kinetic energy of the molecules in
a system.
 A particular molecule does not have a temperature, it has energy.
The gas as a system has temperature.
Energy Transport Mechanism
There are three energy transport mechanisms, any or all of which
may be operating in any given system:
1. heat,
2. Work and
3. mass flow.
 The sign conventions for heat and work are not the same.
 Heat transfer into a system is taken as positive, whereas work must
be produced by or come out of a system to be positive..
Work
 Work is a transient quantity which appears at the boundary when a
system changes its state due to the movement of a part of the
boundary under the action of a force.
 If a system changes its state from state 1 to state 2, then the associated
work can be written as

Where is elementary work between two successive equilibrium

state.
 In mechanics, work is defined as the integral of a force over a
displacement. In mathematical form, work (W) is a scalar quantity
defined according to:

 Unit:: Joule or N-m

  Work can take on a number of forms (e.g., electrical, mechanical,
or magnetic) since it can result from a variety of potential differences.

pdV – work or Displacement work:

 Let, initially the gas in the cylinder be a

system having initially the pressure p1 and
volume V1. The system is in thermodynamic
equilibrium.

 Let the piston moves out to a new final

equilibrium state 2, having the properties p2
and V2.

 At any intermediate point in the travel of

the piston let the pressure be p and volume V.
When the piston moves an infinitesimal distance dl, the infinitesimal
amount of work done by the gas on the piston

Where, dV = a dl = infinitesimal displacement volume

When the piston moves from state 1 to state 2 the total amount of work
 Heat

 Heat is also a transient quantity, which transfer across the boundary

when a system changes its state due to difference in temperature between
the system and surroundings.
 Similarly,

 Unit: Joule
Path function and Point function

 Path functions are functions whose

value depends on the path followed by
the process. These are not the function of
end state of the process.
 Path functions have inexact differential
designated by δ.
Point Function

Point functions are the functions whose have definite value for a given
state.
 Thermodynamic properties are point functions. Point functions have
exact or perfect differential.

 The change in value thus depends on the end states of the system
irrespective of the path the system follows.

 W=f(P,V) => / V(W/ P)  / P(W/ V)