Thermodynamics

Unit-01
Fundamental Concepts
& Definitions
 Unit Outcomes

At the end of this unit the students will be able to-

LO1 Define thermodynamic systems

LO2 Classify thermodynamic systems

Explain various thermodynamic properties, point function and path

LO3
function

LO4 Differentiate between heat and work

 Introduction

 Thermodynamics is the science that deals with the interaction

between energy and material systems.
System, Boundary, Surrounding and Universe
Types of System
Open system:
 The type of system where both mass and heat transfer takes place with
surrounding.
 Example: Boiled water in an open vessel

Closed system:
 The type of system where only heat transfer takes place with surrounding but
there is no mass transfer.
 Example: Boiled water in a closed vessel

Isolated system:
 The type of system where neither heat transfer nor mass transfer takes place.
 Example: Boiled water in thermo flask
Closed system Open system
Adiabatic System:
 An adiabatic system is one which is thermally insulated from its surroundings.
 It can, however, exchange work with its surroundings. If it does not, it becomes
an isolated system.

Homogeneous System:
 A system which consists of a single phase is termed as homogeneous system.
 Examples: Mixture of air and water vapour

Heterogeneous System:
 A system which consists of two or more phases is called a heterogeneous system.
 Examples: Water plus steam, ice plus water and water plus oil.
 Macroscopic & Microscopic Points of View
Thermodynamic studies are undertaken by the following two different approaches.
1. Macroscopic approach (Macro mean big or total)
2. Microscopic approach (Micro means small)

Macroscopic approach:
 In this approach a certain quantity of matter is considered without taking into
account the events occurring at molecular level.
 In other words this approach to thermodynamics is concerned with gross or
overall behaviour. This is known as classical thermodynamics.
 The analysis of macroscopic system requires simple mathematical formulae.
 The values of the properties of the system are their average values.
 The changes in properties can be felt by our senses.
 In order to describe a system only a few properties are needed.
Microscopic approach:
 The approach considers that the system is made up of a very large number of
discrete particles known as molecules. These molecules have different velocities
and energies. The values of these energies are constantly changing with time.
 This approach to thermodynamics which is concerned directly with the structure
of the matter is known as statistical thermodynamics.
 The behaviour of the system is found by using statistical methods as the number
of molecules is very large. So advanced statistical and mathematical methods are
needed to explain the changes in the system.
 The properties like velocity, momentum, impulse, kinetic energy, force of impact
etc. which describe the molecule cannot be easily measured by instruments.
 Our senses cannot feel them.
 Large number of variables are needed to describe a system. So the approach is
complicated.
 Thermodynamic Properties
A property of a system is a characteristic of the system which depends upon its
state, but not upon how the state is reached.

1. Intensive properties:
(i) Those properties which are independent of mass.
(ii) Their values remain uniform throughout system.
(iii) Example: Pressure, temperature, specific volume, density, specific enthalpy
2. Extensive properties:
(i) Those properties which depend on mass.
(ii) Ratio of two extensive properties become an intensive property.
(iii) Example: Enthalpy, entropy, total volume
Examples of Intensive & Extensive Properties
 Thermodynamic Equilibrium
 A system is in thermodynamic equilibrium if the temperature and pressure at all points are
same ; there should be no velocity gradient ; the chemical equilibrium is also necessary.
 Systems under temperature and pressure equilibrium but not under chemical equilibrium
are sometimes said to be in metastable equilibrium conditions.
 Thus for attaining a state of thermodynamic equilibrium the following three types of
equilibrium states must be achieved:
1. Thermal equilibrium: The temperature of the system does not change with time and has
same value at all points of the system.
2. Mechanical equilibrium: There are no unbalanced forces within the system or between
the surroundings. The pressure in the system is same at all points and does not change with
respect to time.
3. Chemical equilibrium: No chemical reaction takes place in the system and the chemical
composition which is same throughout the system does not vary with time.
 Thermodynamic State
 When a system does not undergo any change, all the properties have fixed values. This
condition is known as a thermodynamic state.
 State is the condition of the system at an instant of time as described or measured by its
properties.
 Each unique condition of a system is called a state.
 1-2 represents path where the state changes from 1 to 2.
 Thermodynamic Process

 A process occurs when the system undergoes a change in a state or an energy transfer at
a steady state.
 The series of intermediate states through which a system passes during a process is
called the path of the process.
A process may be non-flow in which a fixed mass within the defined boundary is
undergoing a change of state. Example : A substance which is being heated in a closed
cylinder undergoes a non-flow process.
 Closed systems undergo non-flow processes.
 A process may be a flow process in which mass is entering and leaving through the
boundary of an open system.
 In a steady flow process mass is crossing the boundary from surroundings at entry, and
an equal mass is crossing the boundary at the exit so that the total mass of the system
remains constant.
 Thermodynamic Cycle
 Any process or series of processes whose end states are identical is termed a cycle.
 Fig. shows such a cycle in which a system commencing at condition „1‟ changes in
pressure and volume through a path 123 and returns to its initial condition „1‟.

 Quasi-static process: A quasi-static process is also called a reversible process. This

process is a succession of equilibrium states and infinite slowness is its characteristic
feature.
 Point Function & Path Function
State Functions:
 Those thermodynamic properties which depend on initial and final state.
 e.g.: Pressure, volume, temperature, etc


Path function:
 Those properties which depend on path.
 There are certain quantities which cannot be located on a graph by a point but are given
by the area or so, on that graph.
 e.g.: Heat, Work, Loss of energy due to friction.
 Heat and work are inexact differentials. Their change cannot be written as difference
between their end states.
 Zeroth Law of Thermodynamics

 This law states that if two systems are each equal in temperature to a third, they are equal
in temperature to each other.
 Refer Fig. System „1‟ may consist of a mass of gas enclosed in a rigid vessel fitted with a
pressure gauge. If there is no change of pressure when this system is brought into contact
with system „2‟ a block of iron, then the two systems are equal in temperature (assuming
that the systems 1 and 2 do not react each other chemically or electrically).
 Experiment reveals that if system „1‟ is brought into contact with a third system „3‟ again
with no change of properties then systems „2‟ and „3‟ will show no change in their
properties when brought into contact provided they do not react with each other chemically
or electrically.
 Therefore, „2‟ and „3‟ must be in equilibrium
 Heat & Work
 Heat and work are the forms of energy in transition.
 These are the only forms in which energy can cross the boundaries of a system.
 Neither heat nor work can exist as stored energy.

Work:
 Work is said to be done when a force moves through a distance. If a part of the
boundary of a system undergoes a displacement under the action of a pressure, the work
done W is the product of the force (pressure × area), and the distance it moves in the
direction of the force.
 Work is a transient quantity which only appears at the boundary while a change of state
is taking place within a system. Work is „something‟ 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.
Fig. (a) illustrates this with the conventional piston and cylinder arrangement, the heavy
line defining the boundary of the system.
 Fig. (b) illustrates another way in which work might be applied to a system. A force is
exerted by the paddle as it changes the momentum of the fluid, and since this force moves
during rotation of the paddle work is done.
Sign convention:
 If the work is done by the system on the surroundings, e.g., when a fluid expands pushing a
piston outwards, the work is said to be positive.
i.e., Work output of the system = + W
 If the work is done on the system by the surroundings, e.g., when a force is applied to a
rotating handle, or to a piston to compress a fluid, the work is said to be negative.
i.e., Work input to system = – W
 Heat
 Heat (denoted by the symbol Q), may be, defined in an analogous way to work as
follows: “Heat is „something‟ which appears at the boundary when a system changes its
state due to a difference in temperature between the system and its surroundings”.
 Heat, like work, is a transient quantity which only appears at the boundary while a
change is taking place within the system.

Sign convention:
 If the heat flows into a system from the surroundings, the quantity is said to be positive
and, conversely, if heat flows from the system to the surroundings it is said to be negative.
 In other words :
Heat received by the system = + Q
Heat rejected or given up by the system = – Q.
 Comparison of Work and Heat

Similarities:
(i) Both are path functions and inexact differentials.
(ii) Both are boundary phenomenon i.e., both are recognized at the boundaries of the system as
they cross them.
(iii) Both are associated with a process, not a state. Unlike properties, work or heat has no
meaning at a state.
(iv) Systems possess energy, but not work or heat.
Dissimilarities:
(i) In heat transfer temperature difference is required.
(ii) In a stable system there cannot be work transfer, however, there is no restriction for the
transfer of heat.
(iii) The sole effect external to the system could be reduced to rise of a weight but in the case
of a heat transfer other effects are also observed.
Reversible Work
 Specific Heat
 The specific heat of a solid or liquid is usually defined as the heat required to raise unit
mass through one degree temperature rise.
 For small quantities, we have: dQ = [Link]
where m-mass, C-specific heat, and dT- temperature rise.
 For a gas there are an infinite number of ways in which heat may be added between any
two temperatures, and hence a gas could have an infinite number of specific heats. However,
only two specific heats for gases are defined: Specific heat at constant volume (Cv) and,
Specific heat at constant pressure (Cp).
 dQ = [Link] ------------ For a reversible non-flow process at constant pressure
 dQ = [Link] ------------ For a reversible non-flow process at constant volume
 The values of Cp and Cv, for a perfect gas, are constant for any one gas at all pressures and
temperatures. Hence, integrating above equations, we have
 Flow of heat in a reversible constant pressure process = [Link].(T2 – T1)
 Flow of heat in a reversible constant volume process = [Link].(T2 – T1)
Relation between two specific heats (Cp & Cv)
 Ratio of Specific Heats (Cp & Cv)

Latent Heat
 It is the quantity of heat required to cause a phase change in unit mass of a
substance.
 The temperature of the substance remains constant during phase change.
 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.
 Instruments for measuring ordinary temperatures are known as thermometers and those
for measuring high temperatures are known as pyrometers.
 It has been found that a gas will not occupy any volume at a certain temperature. This
temperature is known as absolute zero temperature.
 The temperatures measured with absolute zero as basis are called absolute temperatures.
 Absolute temperature is stated in degrees centigrade. The point of absolute temperature is
found to occur at 273.15°C below the freezing point of water.
 Absolute temperature = Thermometer reading in °C + 273.15.
 Absolute temperature is degree centigrade is known as degrees kelvin, denoted by “K”.
Measurement of Temperature
 1. Expansion Thermometers
Liquid-in-glass thermometer:
 This is a very familiar type of thermometer.
 The mercury or other liquid fills the glass bulb and extends into the bore of
the glass stem. Mercury is the most suitable liquid and is used from – 38.9°C
(melting point) to about 600°C.
 The thermometers employed in the laboratory have the scale engraved directly
on the glass stem.
 A usual type of mercury-in-glass thermometer is shown in Fig..
 An expansion bulb is usually provided at the top of the stem to allow room for
expansion of mercury, in case the thermometer is subjected to temperature
above its range.
 The upper limit for mercury-in-glass thermometers is about 600°C. As the
upper limit is far above the boiling point of mercury, some inert gas i.e.,
nitrogen is introduced above the mercury to prevent boiling.
Bimetallic thermometers:
 In a bimetallic thermometer differential expansion of bimetallic strips is used to indicate
the temperature.
 It has the advantage over the liquid-in-glass thermometer, that it is less fragile and is
easier to read.
 In this type of thermometer two flat strips of different metals are placed side by side and
are welded together.
 Many different metals can be used for this purpose. Generally one is a low expanding
metal and the other is high expanding metal.
 The bimetal strip is coiled in the form of a spiral or helix. Due to rise in temperature, the
curvature of the strip changes.
 The differential expansion of a strip causes the pointer to move on the dial of the
thermometer.
 2. Pressure Thermometers

 In pressure thermometers liquids, gases and vapours can all be used.

 The principle on which they work is quite simple. The fluid is confined in a closed system.
 In this case the pressure is a function of the temperature, so that when the fluid is heated,
the pressure will rise. And the temperature can be indicated by Bourdon type pressure gauge.
 In general, the thermometer consists of a bulb which contains bulk of the fluid.
 The bulb is placed in the region whose temperature is required.
 A capillary tube connects the bulb to a Bourdon tube, which is graduated with a
temperature scale.
i. Vapour pressure thermometer: A schematic diagram of a vapour pressure thermometer
is shown in Fig.. When the bulb containing the fluid is installed in the region whose
temperature is required, some of the fluid vapourizes, and increases the vapour pressure.
This change of pressure is indicated on the Bourdon tube. The relation between
temperature and vapour pressure of a volatile liquid is of the exponential form.
Therefore, the scale of a vapour pressure thermometer will not be linear.
ii. Liquid-filled thermometer: A liquid-filled thermometer is shown in Fig.. In this case,
the expansion of the liquid causes the pointer to move in the dial. Therefore liquids
having high co-efficient of expansion should be used. In practice many liquids e.g.,
mercury, alcohol, toluene and glycerine have been successfully used. The operating
pressure varies from about 3 to 100 bar. These type of thermometers could be used for a
temperature up to 650°C in which mercury could be used as the liquid. In actual design,
the internal diameter of the capillary tube and Bourdon tube is, made much smaller than
that of the bulb. This is because the capillary tube is subjected to a temperature which is
quite different from that of the bulb. Therefore, to minimise the effect of variation in
temperature to which the capillary tube is subjected, the volume of the bulb is made as
large as possible as compared with the volume of the capillary. However, large volume
of bulb tends to increase time lag, therefore, a compensating device is usually built into
the recording or indicating mechanism, which compensates the variations in temperature
of the capillary and Bourdon tubes.
Liquid-filled thermometer
iii. Gas-filled thermometers:
 The temperature range for gas thermometer is practically the same as that of liquid filled
thermometer.
 The gases used in the gas thermometers are nitrogen and helium. Both these gases are
chemically inert, have good values for their co-efficient of expansion and have low specific
heats.
 The construction of this type of thermometer is more or less the same as mercury-
thermometer in which Bourdon spring is used.
 The only difference in this case is that bulb is made much larger than used in liquid-filled
thermometers.
 For good performance the volume of the bulb should be made at least 8 times than that of
the rest of the system.
 These thermometers are generally used for pressures below 35 bar.
 3. Thermocouple Thermometers
 For higher range of temperature i.e., above 650°C, filled thermometers are unsuitable.
 For higher range of temperature, thermocouples and pyrometers are used.
 In its simplest form a thermocouple consists of two dissimilar metals or alloys which
develop e.m.f. when the reference and measuring junctions are at different temperatures.
 The reference junction or cold junction is usually maintained at some constant
temperature, such as 0°C.

Fig. shows a simple circuit of a thermocouple and the temperature measuring device.
 In many industrial installations the instruments are equipped with automatic
compensating devices for temperature changes of the reference junction, thus eliminating
the necessity of maintaining this junction at constant temperature.
 4. Radiation Pyrometers
 A device which measures the total intensity of radiation emitted from a body is called
radiation pyrometer.
 The elements of a total radiation pyrometer are illustrated in Fig.
 It collects the radiation from an object (hot body) whose temperature is required.
 A mirror is used to focus this radiation on a thermocouple. This energy which is
concentrated on the thermocouple raises its temperature, and in turn generates an e.m.f.
 This e.m.f. is then measured either by the galvanometer or potentiometer method. Thus
rise of temperature is a function of the amount of radiation emitted from the object.
Advantages of the pyrometers:
1. The temperatures of moving objects can be measured.
2. A higher temperature measurement is possible than that possible by thermocouples etc.
3. The average temperatures of the extended surface can be measured.
4. The temperature of the objects which are not easily accessible can be measured.
 5. Optical Pyrometer
 An optical pyrometer works on the principle that matters glow above 480°C and the
colour of visible radiation is proportional to the temperature of the glowing matter.
 The amount of light radiated from the glowing matter (solid or liquid) is measured and
employed to determine the temperature.
 Fig. shows a disappearing filament pyrometer.
Operation :
 The optical pyrometer is sighted at the hot body and focused.
 In the beginning filament will appear dark as compared to the background which is bright
(being hot).
 By varying the resistance (R) in the filament circuit more and more current is fed into it,
till filament becomes equally bright as the background and hence disappears.
 The current flowing in the filament at this stage is measured with the help of an ammeter
which is calibrated directly in terms of temperature.
 If the filament current is further increased, the filament appears brighter as compared to
the background which then looks dark.
 An optical pyrometer can measure temperatures ranging from 700 to 4000°C.