PHY115 – Physics V

UNIT-3

“Thermodynamics is the branch of physical science that deals with the various phenomena of
energy and related properties of matter, especially of the laws of transformations of heat into other
forms of energy and vice-versa.”

1.1 MACROSCOPIC AND MICROSCOPIC APPROACHES:

For analyzing any system there are basically two approaches available in thermodynamics.
Approach of thermodynamic analysis means how the analyzer considers the system. Macroscopic
approach is the one in which complete system as a whole is considered and studied without caring for
what is there constituting the system at microscopic level.
Contrary to this the microscopic approach is one having fragmented the system under
consideration upto microscopic level and analyzing the different constituent
subsystems/microsystems. In this approach study is taken at the microscopic level. For studying the
system the microlevel studies are put together to see the influences on overall system. Thus, the
statistical techniques are used for integrating the studies made at microscopic level. This is how the
studies are taken up in statistical thermodynamics. In general it can be said that,
Macroscopic approach analysis = Σ (Microscopic approach analysis).

1.2 UNITS COMMONLY USED:

Temperature: Standard unit of temperature is Kelvin. However, 0Celcius and 0Fahrenheit are also
widely used. The conversion formula is:
5
TC  (TF  32)  TK  273
9
Further study: https://en.wikipedia.org/wiki/Conversion_of_units_of_temperature

Volume: Standard unit of volume is metre3. We also use mililitre (= 10-3litre = 1cc = 1 cubic
centimeter). Also, 1 metre3 = 100 cm x 100 cm x 100 cm = 1000 x 1000 cm3 = 1000 litre

Pressure: Pressure at any point is defined as the normal force per unit area, so if the normal force is
F and area is A then pressure, p = F/A. In SI system, units of the pressure is Newton/metre 2 . This
N/m2 is also termed as Pascal (Pa). Hence one Pascal (1 Pa) is equal to the force of one Newton acting
on one square metre area. Pressure also has unit of ‘bar’ in SI system and the equivalence is given as:
1 bar = 105 Pa = 0.1 MPa = 100 kPa.

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Here 1 MPa = 106 Pa and 1 kPa = 103 Pa.

For hydrostatic pressure unit of pressure used is “torr”. This one torr is defined as pressure exerted by
column of 1 mm Hg.
1 mm Hg = 1 torr = 133 Pa
Standard atmospheric pressure of 1 atm is the pressure produced by a column of mercury of 760 mm
height. Standard atmospheric pressure, 1 atm = 760 mm Hg = 101325 Pa = 1.01325 bar

1.3 SYSTEMS, SURROUNDINGS AND UNIVERSE:

In thermodynamics the ‘system’ is defined as the quantity of matter or region in space upon
which the attention is concentrated for the sake of analysis. These systems are also referred to as
thermodynamic systems. For the study these systems are to be clearly defined using a real or
hypothetical boundary. Every thing outside this real/hypothetical boundary is termed as the
‘surroundings’. Thus, the surroundings may be defined as every thing surrounding the system. System
and surroundings when put together result in universe.

Universe = System + Surroundings

The system is also some times defined as the control system and the boundary defined
for separating it from surroundings is called control boundary, the volume enclosed within the
boundary is control volume and the space enclosed within the boundary is called control space.
Based on the energy and mass interactions of the systems with surroundings/other
systems across the boundary the system can be further classified as the open, closed, and isolated
system. The ‘open system’ is one in which the energy and mass interactions take place at the
system boundary, for example, automobile engine etc. ‘Closed system’ is the system having only
energy interactions at its boundary, for example, Boiling water in a closed pan etc. The mass
interactions in such system is absent. ‘Isolated system’ refers to the system which neither has
mass interaction nor energy interaction across system boundary, for example, Thermos Flask etc.
Thus, the isolated system does not interact with the surroundings/systems in any way.

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1.4 PROPERTIES AND STATE:

For defining any system certain parameters are needed. ‘Properties’ are those observable
characteristics of the system which can be used for defining it. Thermodynamic properties are the
observable characteristics of the thermodynamic system. Pressure, temperature, volume, viscosity,
modulus of elasticity etc. are the examples of property. These properties are some times observable
directly and some times indirectly.
Properties can be further classified as the intensive property and extensive property. The
intensive properties are those properties which have same value for any part of the system or the
properties that are independent of the mass of system are called intensive properties, e.g., pressure,
temperature etc. Extensive properties on the other hand are those which depend upon the mass of
system and do not maintain the same value for any part of the system, e.g., mass, volume, energy,
enthalpy etc. These extensive properties when estimated on the unit mass basis result in intensive
property which is also known as specific property, e.g., specific heat, specific volume, specific
enthalpy etc.
‘State’ of a system indicates the specific condition of the system. To know the characteristics
of the system quantitatively refers to knowing the state of system. Thus, when the properties of system
are quantitatively defined then it refers to the state. For completely specifying the state of a system
number of properties may be required which depend upon the complexity of system. Thermodynamic
state in the same way refers to the quantitative definition of the thermodynamic properties of a
thermodynamic system e.g., for defining a gas inside the cylinder one may have to define the state

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using pressure and temperature as 12 bar, 298 K. When the thermodynamic properties defining a state
undergo a change in their values it is said to be the ‘change of state’.
These thermodynamic states could be defined based on certain minimum number of properties
which are called “independent properties”. Such as for specifying the state of gas of mass ‘m’ in a
cylinder we need to know its pressure ‘p’ and specific volume ‘v’ or alternatively by knowing pressure
‘p’ and temperature ‘t’ or by knowing temperature ‘t’ and specific volume ‘v’ etc. Thus, p and v or p
and t or t and v are two independent properties of system. Other remaining properties can be
determined in terms of these independent properties. The number of independent intensive properties
required for defining intensive state of system depends upon its complexity. The complexity of system
means the number of phase and number of types of its interaction with surrounding.
The minimum number of independent intensive properties which can be changed without changing
phase, chemical constituents etc. are called “degree of freedom” of system. Degree of freedom (F)
of a system can be given by following empirical relation known as Gibbs phase rule.
F = C+2–ϕ
where C refers to the number of components and ϕ is the number of phase present in system.

1.5 THERMODYNAMIC PATH, PROCESS AND CYCLE:

Thermodynamic system undergoes changes due to the energy and mass interactions.
Thermodynamic state of the system changes due to these interactions. The mode in which the change
of state of a system takes place is termed as the process such as constant pressure, constant
volume process etc. Let us take gas contained in a cylinder and being heated up. The heating of gas in
the cylinder shall result in change in state of gas as it’s pressure, temperature etc. shall increase.
However, the mode in which this change of state in gas takes place during heating shall be constant
volume mode and hence the process shall be called constant volume heating process.
The path refers to the series of state changes through which the system passes during a process.
Thus, path refers to the locii of various intermediate states passed through by a system during a process.
(see Fig. 1.2).
Cycle refers to a typical sequence of processes in such a fashion that the initial and final states
are identical. Thus, a cycle is the one in which the processes occur one after the other so as to finally
land the system at the same state. Thermodynamic path in a cycle is in closed loop form. After the
occurrence of a cyclic process, system shall show no sign of the processes having occurred.
Mathematically, it can be said that the cyclic integral of any property in a cycle is zero, i.e

 dp  0 , where p is any thermodynamic property.

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1.6 THERMODYNAMIC EQUILIBRIUM:

Equilibrium is that state of a system in which the state does not undergo any change in itself
with passage of time without the aid of any external agent. Equilibrium state of a system can be
examined by observing whether the change in state of the system occurs or not. If no change in state
of system occurs then the system can be said in equilibrium. Thermodynamic equilibrium is a situation
in which thermodynamic system does not undergo any change in it’s state. Let us consider a steel glass
full of hot milk kept in open atmosphere. It is quite obvious that the heat from the milk shall be
continuously transferred to atmosphere till the temperature of milk, glass and atmosphere are not alike.
During the transfer of heat from milk the temperature of milk could be seen to decrease continually.
Temperature attains some final value and does not change any more. This is the equilibrium state at
which the properties stop showing any change in themselves.
Generally, thermodynamic equilibrium of a system may be attained by ensuring the
mechanical, thermal, chemical and electrical equilibriums of the system. Mechanical equilibrium of
the system can be well understood from the principles of applied mechanics which say that the net
force and moment shall be zero in case of such equilibrium. Thus, in the state of mechanical
equilibrium the system does not have any tendency to change mechanical state as it is the state at which
the applied forces and developed stresses are fully balanced.

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 Thermal equilibrium is that equilibrium which can be stated to be achieved in the absence of
any heat interactions. Thus, if the temperature states of the system do not change then thermal
equilibrium is said to be attained. Equality of temperature of the two systems interacting with each
other shall ensure thermal equilibrium.
Chemical equilibrium is the one which can be realized in case the chemical potential of the
systems interacting are same. The equality of forward rate of chemical reaction and backward rate of
chemical reaction can be taken as criterion for ensuring the chemical equilibrium. Similar to this, in
case the electrical potential of the systems interacting are same, the electrical equilibrium is said to be
attained.
Thus, a system can be said to be in thermodynamic equilibrium if it is in mechanical, thermal,
chemical and electrical equilibrium.

1.7 REVERSIBILITY AND IRREVERSIBILITY:

Thermodynamic processes may have the change of state occurring in two ways. One is the
change of state occurring so that if the system is to restore its original state, it can be had by reversing
the factors responsible for occurrence of the process. Other change of state may occur such that the
above restoration of original state is not possible. Thermodynamic system that is capable of restoring
its original state by reversing the factors responsible for occurrence of the process is called
reversible system and the thermodynamic process involved is called reversible process. Thus upon
reversal of a process there shall be no trace of the process being occurred, i.e. state changes during the
forward direction of occurrence of a process are exactly similar to the states passed through by the
system during the reversed direction of the process. It is quite obvious that such reversibility can be
realized only if the system maintains its thermodynamic equilibrium throughout the occurrence of
process. The irreversibility is the characteristics of the system which forbids system from retracing the
same path upon reversal of the factors causing the state change. Thus, irreversible systems are those
which do not maintain equilibrium during the occurrence of a process. Various factors responsible for
the non-attainment of equilibrium are generally the reasons responsible for irreversibility. Presence of
friction, dissipative effects etc. have been identified as a few of the prominent reasons for
irreversibility. (see Fig. 1.3)
At the same time, in broader aspect, anything happening in universe is reversible if it completes
in cycle and doesn’t leave any change in the universe. However, such processes are practically
impossible.

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1.8 QUASI-STATIC PROCESS:

Thermodynamic equilibrium of a system is very difficult to be realized during the occurrence

of a thermodynamic process. It may be understood that this kind of equilibrium is rather practically
impossible. In case such equilibrium could not be attained then the thermodynamic analysis cannot be
done, as the exact analysis of a system not in equilibrium is impossible. ‘Quasi-static’ consideration is
one of the ways to consider the real system as if it is behaving in thermodynamic equilibrium and thus
permitting the thermodynamic study. Actually system does not attain thermodynamic equilibrium,
only certain assumptions make it akin to a system in equilibrium for the sake of study and analysis.
Quasi-static literally refers to “almost static” and the infinite slowness of the occurrence of a
process is considered as the basic premise for attaining near equilibrium in the system. Here it is
considered that the change in state of a system occurs at infinitely slow pace, thus consuming very
large time for completion of the process. During the dead slow rate of state change the magnitude of
change in a state shall also be infinitely small. This infinitely small change in state when repeatedly
undertaken one after the other results in overall state change but the number of processes required for
completion of this state change are infinitely large. Quasi-static process is presumed to remain in
thermodynamic equilibrium just because of infinitesimal state change taking place during the
occurrence of the process. Quasi static process can be understood from the following example.
Let us consider the heating of gas in a container with certain mass ‘W’ kept on the top lid (lid
is such that it does not permit leakage across its interface with vessel wall) of the vessel as shown in
Fig. 1.4. After certain amount of heat being added to the gas it is found that the lid gets raised up.
Thermodynamic state change is shown in figure. The “change in state” is significant. During the
“change of state” since the states could not be considered to be in equilibrium, hence for

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unsteady state of system, thermodynamic analysis could not be extended. Difficulty in thermodynamic
analysis of unsteady state of system lies in the fact that it is not sure about the state of system as it is
continually changing and for analysis one has to start from some definite values. Let us now assume
that the total mass comprises of infinitesimal small masses of ‘w’ such that all ‘w’ masses put together
become equal to W. Now let us start heat addition to vessel and as soon as the lifting of lid is observed
put first fraction mass ‘w’ over the lid so as to counter the lifting and estimate the state change. During
this process it is found that the state change is negligible. Let us further add heat to the vessel and again
put the second fraction mass ‘w’ as soon as the lift is felt so as to counter it. Again the state change is
seen to be negligible. Continue with the above process and at the end it shall be seen that all fraction
masses ‘w’ have been put over the lid, thus amounting to mass ‘W’ kept over the lid of vessel and the
state change occurred is exactly similar to the one which occurred when the mass kept over the lid was
‘W’. In this way the equilibrium nature of system can be maintained and the thermodynamic analysis
can be carried out. p-V representation for the series of infinitesimal state changes occurring
between states 1 & 2 is also shown in Fig. 1.4.

1.9 ZEROTH LAW OF THERMODYNAMICS:

The Zeroth Law of Thermodynamics states that if two bodies are each in thermal equilibrium with
some third body, then they are also in equilibrium with each other. Thermal equilibrium means that
when two bodies are brought into contact with each other and separated by a barrier that is permeable
to heat, there will be no transfer of heat from one to the other.

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We can also conclude that:
"Two systems which are equal in temperature to a third system are equal in temperature to each other".
This is the Zeroth Law of Thermodynamics and provides the basis for temperature measurements.

1.10 TEMPERATURE SCALES:

Consider an experiment involving three systems S1, S2 and S3. Suppose we bring S3 into contact with
S1 until they reach thermal equilibrium.

No work interactions assumed. Now if we bring S3 into contact with S2 and as a result observable
changes occur in S3¸ then we can conclude that the temperatures of S1 and S2 are unequal. To measure
this inequality we use a thermometer. For thermometer, we can use any property that changes with
temperature. For example, if we chose a glass tube containing mercury as system S3, then we would
have a mercury in glass thermometer. The mercury in glass thermometer is usually calibrated between
two fixed points- one at the melting point of ice and the other at the boiling point of water- both at the
pressure of one atmosphere. Temperature scales are then defined by assigning numbers to the ice point
and steam point and to the equally-spaced points between them.
Celsius or centigrade : Ice point: 0 deg C. Steam point: 100 deg C, with 100 equal subdivisions.
Farenheit: Ice point: 32 deg F. Steam point: 212 deg F, with 180 equal subdivisions.

Other thermometers: 1. Constant volume thermometer, gives a very close result to the thermodynamic
temperature scale which is not based on a particular thermometric substance.
2. Platinum resistance thermometer

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1.11 INTERNAL ENERGY and TEMPERATURE:

Internal energy (also called thermal energy) is the energy of an object or substance is due to
the kinetic and potential energies associated with the random motions of all the particles that make it
up. The kinetic energy is, of course, due to the motion of the particles. To understand the potential
energy, imagine a solid in which all of its molecules are bound to its neighbors by springs. As the
molecules vibrate, the springs are compressed and stretched. (Liquids and gases are not locked in a
lattice structure like this.). The hotter something is, the faster its molecules are moving or vibrating,
and the higher its temperature. Temperature is proportional to the average kinetic energy of the atoms
or molecules that make up a substance.

Internal energy vs Heat: The term heat refers is the energy that is transferred from one body or
location due to a difference in temperature. This is similar to the idea of work, which is the energy that
is transferred from one body to another due to forces that act between them. Heat is internal energy
when it is transferred between bodies.
Technically, a hot potato does not possess heat; rather it possesses
a good deal of internal energy on account of the motion of its molecules. If that potato is dropped in
a bowl of cold water, we can talk about heat: There is a heat flow (energy transfer) from the hot potato
to the cold water; the potato’s internal energy is decreased, while the water’s is increased by the same
amount.

Internal vs External energy: Suppose a 1 kg block of ice is sliding at 7 m/s. This is the speed of the
center of mass of the block, not the speed of each individual water molecule. To calculate the total
kinetic energy of the water molecules of the block directly, we would have to know the speed of each
molecule as it vibrates, all 33.4 trillion trillion of them! (In practice we would just measure the
temperature & mass of the ice.) The internal energy of the ice does not depend on the motion of the
whole body relative to Earth. What matters is the motion of the molecules in the reference frame of
the block. Otherwise, it would be impossible for a cold object to move quickly or a hot one to move
slowly. Note: If friction is present, it could do work on the ice and convert some of the “uniform”
kinetic energy of the block into “random” kinetic energy of its molecules (internal energy).
Regardless, the total energy of the block is the kinetic energy of the center of mass + the internal energy

Temperature vs internal energy: Temperature and internal energy are related but not the same thing.
Temperature is directly proportional to the average molecular kinetic energy (true for gases,
approximately true for solids and liquids whose molecules interact with each other more). Note the
word average is used, not total.

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 Consider a bucket of hot water and a swimming pool full of cold water. The hot water is at a
higher temperature, but the pool water actually has more internal energy! This is because, even though
the average kinetic energy of the water molecules in the bucket is much greater than that of the pool,
there are thousands of times more molecules in the pool, so their total energy is greater.
It’s analogous to this: A swarm of 1000 slow moving bees could have more total kinetic energy
than a dozen fast moving, hyperactive bees buzzing around like crazy. One fast bee has more kinetic
energy than a slow one, but there are a lot more slow ones.

Absolute zero and Kelvin scale: The Kelvin scale is setup so that its zero point is the coldest possible
temperature--absolute zero, at which point a substance would have zero internal energy. This is -
273.15 °C, or -459.69 °F. Absolute zero can never be reached, but there is no limit to how close we
can get to it. Scientists have cooled substances to within 10-5 kelvins of absolute zero. How do we
know how cold absolute zero is, if nothing has ever been at that temperature? The answer is by
graphing Pressure vs. Temperature for a variety of gases and extrapolating.

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