GET206: Fundamentals of Thermodynamics/EGR2205: Thermodynamics I

Week 2
Basic Definitions in Thermodynamics, Heat and Work

1.1 System and Surroundings

A Thermodynamic system is defined as a quantity of matter or a region in space whose behaviour is being
investigated.

Surrounding is everything external to the system or a region outside the system. In it’s usual context the term
‘surroundings’ is restricted to the regions in the immediate vicinity which has a detectable influence on the
system.

Boundary is the real or imaginary surface which separates the system from its surroundings. It may be fixed or
moving. Mathematically speaking, the boundary has zero thickness, and thus it can neither contain any mass
nor occupy any volume in space.

Figure 1.2 Thermodynamic System, Boundary, Surrounding

1.1.1 Types of Thermodynamic Systems

There are three types of thermodynamic systems:

a) Closed System (control mass): In closed system, attention is focused on a fixed mass. Energy in the form of
heat and work (The terms heat and work will be defined in the subsequent section.) can cross the boundary
of the system. But there is no mass flow across the boundary. Hence, the possibility of change in volume is
always there in the closed systems.

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 Let us consider a piston cylinder device as as shown below and we want to find out what happens to the
enclosed gas when it is heated.

• The gas is the system (since our attention is focused on the gas)
• The inner surface of the piston and cylinder forms the boundary
• Everything outside the gas including the piston and cylinder is the surrounding

Mass cannot cross the boundary so it is a closed system but Energy can cross the boundary and part of the
boundary may move (volume can change)

b) Open System: In open system, both matter and energy can cross the boundary. Here, the behaviour of a
fixed region in space called control volume is investigated and hence, there is no change in volume. The
surface of the control volume is known as control surface. Flow through various engineering devices such as
compressor, turbine, nozzle, water heater, car radiator are best studied by selecting a region within the device
as the control volume since they involve mass flow in and out of the system. Boundaries of a control volume
are called control surfaces.

A simple example of an open system is water heater. Let us say we want to determine how much heat we
must transfer to the water in the tank in order to supply a steady stream of hot water. Since hot water will
leave the tank and be replaced by cold water, we cannot choose a fixed mass as our system for analysis.

Instead we must concentrate on the fixed volume formed by the interior surface of the tank and consider the
hot and cold water streams as mass leaving and entering the control volume.
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c) Isolated System: A system that exchanges neither energy nor matter with its surroundings. Is a special type
of closed system.

1.2 State and Property of a system

The term state is used to signify the condition of a system at a specific instant. The characteristics which can
be used to describe the condition of the system are known as properties. Or Property can also be defined as
those observable macroscopic quantities which are definable at any particular instant without reference to the
system history. To describe a system state, all the values of the properties must be given.

Example 1: Let us consider two vehicles A and B located at two different cities. The straight line distance between
A and B is thus a property of the system because the value is fixed only by the location of the vehicles at the
specified time and not by the manner they arrived their locations. But the distance travelled by vehicle A in
reaching vehicle B depends on how vehicle A travels. The distance travelled is known if we know the history of
the trip i.e the route followed. Thus distance travelled cannot be property of the system. However, we can say
that the distance travelled is greater than or equal to the straight line distance between the two vehicles. We can
also compute the straight line distance (property) from the history of the trip (route followed).

Example 2: Consider an automobile tire. The depth of the tire thread is a property but the number of miles
travelled is not since there is no direct correlation between the number of miles travelled and the condition of the
tire since this depends on the type of road and load of the automobile (history).

In thermodynamics properties include: pressure, mass, volume, density, temperature, internal energy,
enthalpy and entropy, charge, voltage, force, position, and velocity.

In thermodynamics the common non-properties are heat transfer and work transfer.

Properties can be classified as either independent or dependent. They can also be classified into two categories:
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 • Intensive: properties which are independent of quantity of matter or mass
• Extensive: properties are dependent on quantity of matter or mass

Consider a vessel containing air. If a membrane is assumed to be introduced into the vessel such that it divides
the vessel into two equal parts. The properties remaining unchanged such as pressure and temperature are
intensive properties. Volume of air will be reduced to half of its initial value. Hence, it is an extensive property.

1.3 Equilibrium

The word equilibrium means balance. An equilibrium state of a thermodynamic system is a state that cannot be
changed without any interaction with its surroundings.

The factors that cause a change without any interactions with its surroundings are:

a) Pressure difference
b) Temperature difference
c) Chemical reaction

If a system is balanced in all respects, it is in a state of thermodynamic equilibrium.

Balanced in all respects means:

• There should not be any temperature difference within the system, so that the system is thermally
balanced.
• No pressure difference exists between any two points within the system (Neglecting gravitational effects)
and between the system and surroundings, so that it is mechanically balanced.
• No chemical reaction is taking place, so that it is chemically balanced.
• If two phases are involved, mass of each phase remains constant so that phase equilibrium is achieved.

Hence, for a system in a state of thermodynamic equilibrium, there is no change in any macroscopic property.

1.3.1 State Postulate

As mentioned earlier, properties are meant for describing the state of a system. To fix a state, all the properties
need not be specified. If any two independent intensive properties are specified, rest of the properties
automatically assumes certain values. This is known as state postulate.

Two properties are independent if one property can be varied while the other one is held constant. For example
Temperature and specific volume are always independent properties and together they can fix the state of a
simple compressible system.

1.4 Processes and Cycles

When a system is taken from one equilibrium state to another, the change is known as process. The series of
intermediate states through which a system passes during a process is called the path of the process. If all these
intermediate states are equilibrium states, the process is known as quasi equilibrium or quasi-static process.

To describe a process completely, the initial and final states of the process, as well as the path and the
interactions with the surroundings needs to be specified.

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Consider a certain quantity of gas taken in a frictionless piston cylinder arrangement as shown below. The system
is in thermodynamic equilibrium so that there is no unbalanced force acting on piston.

Fig.1.3 Illustration for thermodynamic equilibrium

The moment the weight is removed from the piston, mechanical equilibrium does not exist and as a result the
piston is moved upward until mechanical equilibrium is restored again. Therefore the actual process occurs only
when equilibrium does not exist.

As shown in Fig.1.3.a, if the entire weight on the piston is removed at once, the deviation from the equilibrium is
high and the expansion is rapid. For such a process the intermediate states are not equilibrium states and hence
the process would be non-quasi equilibrium.

If the weight is assumed to be made of a large number of small pieces as shown in Fig.1.5.b and taken off one
by one, the deviation from equilibrium is less. The process could be considered quasi-equilibrium.

A thermodynamic system is said to undergo a cycle, if it is taken through a number of processes such that, the
final state of the last process is identical with the initial state of the first process in in all respects. For cycles net
change in any property is zero.

1.5 Energy Transfer (Interaction between System and Surrounding)

We have already mentioned that energy can cross the boundary of a closed system in the form of either Heat or
Work (Figure 2.2).

1.5.1 What is Heat

From experience we know that if we put a can of cold soft drink (Pepsi) on a table it eventually warms up and if
we put a cup of hot tea on the same table it eventually cools down. This means that when a body is left in a

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medium that is at different temperature, energy transfer takes place between the body and the surrounding
medium. The direction of the energy transfer is always from higher temperature object to the lower temperature
object. This energy transfer is called heat

Figure 2.2 Energy transfer from a closed system

Heat is thus defined as the interaction between two systems (or system and surrounding) which occurs by virtue
of their temperature difference.

Heat is energy in transition and is recognised only at the boundary of the system. Consider a hot baked potato
as shown in figure 2.3. The potato contains thermal energy; this energy is heat transfer only as it passes through
the skin of the potato (system boundary) to reach the air. Once in the surrounding, the transferred heat becomes
part of the internal energy of the surroundings. Thus in thermodynamics, the term heat simply means heat
transfer.

Figure 2.3 Heat and thermal energy

A process during which there is no heat transfer is called an adiabatic process. This can be achieved in two
ways: either the system is well insulated so that only a negligible amount of heat can pass through the boundary
or both the system and the surrounding are at the same temperature. Adiabatic process should not be confused
with an isothermal process. Although there is no heat transfer in an adiabatic process, the temperature and
energy content of the system can still be changed by other means such as work.

The amount of heat transferred during a process between two states (states 1 and 2) is denoted by Q 12 or just
Q. heat transfer per unit mass is denoted by q and is determined from:

𝑄
𝑞= (𝑘𝐽/𝑘𝑔)
𝑚

The amount of heat transfer per unit time is called the rate of heat transfer and is denoted by 𝑄̇ having a unit of
kJ/s which is equivalent to kW.

The amount of heat transfer is during a process is given by:

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 𝑡2
𝑄 = ∫ 𝑄̇ 𝑑𝑡 (𝑘𝐽)
𝑡1

If 𝑄̇ remains constant during the process, the relation reduces to:

𝑄 = 𝑄̇ ∆𝑡 (𝑘𝐽)

Where ∆𝑡 = 𝑡2 − 𝑡1 is the time interval during which the process takes place.

The relationship between q, Q and 𝑄̇

1.5.2 What is Work

Work is an energy interaction between a system and its surrounding. Any energy interaction that is not caused
by temperature difference between a system and its surrounding is work.

Work is done when the point of application of a force moves in the direction of the force. The product of the force
and the distance moved in the direction of the force is equals to the amount of the work done.

Thus we can define work as: Something which appears at the boundary when a system changes its state due to
the movement of part of the boundary under the action of a force.

When a boundary of a closed system moves in the direction of the force acting on it, then the surroundings do
work on the system. When the boundary is moved outwards the work is done by the system on its surrounding.

The unit of work is Nm or J the rate of doing work is called power in J/s or W. Work done during a process is
denoted by W12, or simply W. Work done per unit mass of a system is denoted by wand expressed as:

𝑊
𝑤= (𝑘𝐽/𝑘𝑔)
𝑚

The work done per unit time is called power and denoted by 𝑊̇ and the unit of power is kJ/s or kW.

1.5.3 Sign Convention of Heat and Work

Work and heat are directional quantity, thus its description requires specification of both magnitude and direction.

Thus we must adopt a formal sign convention.

• Heat transfer to a system and work done by a system are positive.

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 • Heat transfer from a system and work done on a system are negative.

Another way is to use subscripts in and out to indicate the direction as shown in figure 2.4.

Figure 2.4 Sign convention

1.5.4 Comparison between work and heat

• Both heat and work are boundary phenomena, that is, they occur only at the boundary.
• Systems possess energy not heat and work.
• Both are associated with a process, not a state, Unlike properties
• Both work and heat are path functions, that is, they are inexact differentials.

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