Module 2

First Law of Thermodynamics:

Statement of the First law of thermodynamics,
The first law of thermodynamics states that "When a closed system executes a cyclic process, the
algebraic sum of work transfer is proportional to the algebraic sum of heat transfer". Since the
system at the end of a cycle experiences no net change, the algebraic sum of heat andwork during a
cycle is zero.

Symbolically,

In the above equation, the symbol ∮ designates the cyclic integraL and δ designates work and heat
are inexact differentials. The above equation can also be written as

where δQ represents infinitesimal heat transferred

Extension of the First law to non-cyclic process,

Energy as a property ( THE FIRST LAW OF THERMODYNAMICS FOR A CHANGE

IN STATE OF A CLOSED SYSTEM)
As per the definition of first law, it is applied to a closed system undergoing a cycle: But, we can
apply the law for a closed system undergoing a change of state by introducing new property E.

Consider a system. Undergoing a cycle changing its state from 1 to state 2 by process A as shown in
the figure 3.2

From the first law of thermodynamics,

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Considering two separate processes changing from state 1 to state 2 by process A and then returning
to state I by process B. For this cycle we can write

--(1)

Now consider another cycle, the system changes its state from to 2 by process A, and then returns.
to state I by process C. For this cycle we can write,

--(2)

Substituting (2) from (I), we have

On rearranging,

--(3)
Since Band C are two arbitrary processes between states 2 and 1, the quantity (oQ - oW) remains
same for all processes between the two states.

Thus, (δQ - δW) depends only on the initial and final states and not on the path followed between
the two states. Hence (δQ - δW) is a point function and is a property of the system. This property is
known as internal energy and is denoted by E

Thus, we can write

Modes of energy,( Physical significance of E)

The property E represents the sum of energy transfers across the system boundary known as stored
energy. This energy might be present in a variety of forms namely, kinetic energy, potential energy,
chemical energy, electrical energy, energy associated with the movement and position of the
molecules etc.

However, in thermodynamics it is convenient to consider kinetic and potential energies separately

and club all other types of stored energy in a single term known as internal energy U. Thus, we can
write

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 E = Internal energy + Kinetic energy + Potential energy --- (6)

Or

E = U + KE+ PE

Since all these energies are thermodynamic properties, we can write,

dE = dU + d(KE) + d(PE) --(7)

Substituting (7) in (4), we have,

δQ = dU + d(KE) + d(PE) + δW ---(8)

In the absence of motion and gravity effect, the aboveO equation reduces to,

δQ = dU + δW --- (9)

The above equation (9) is known as Non-Flow Energy Equation and is abbreviated as N.F.E.E.

Enthalpy
The sum of internal energy and the pressure –volume product consists entirely of properties which is
known as Enthalpy. It is an extensive property and is denoted by symbol H

Thus H= U+pV

Pure substance
Pure substance is one which exists only in one species irrespective of phase or planes which it
exists.A pure substance can exist in three different states. It is defined as the having one chemical
composition or structure but capable of existing in more than one phase

Internal energy and enthalpy of pure substance

The internal energy of a pure substance can be expressed by using a two property rule. It is denoted
by letter U. Internal energy is directly influenced by heat interactaions. In the absence of motion,
caapalirity, gravity, electricity and magnetism, the change in internal energy of a pure substance
between two states 1 and 2 can be determined as follows

From first law of thermodynamics, for unit mass of a substance,

1q2 – 1W2 =Δu12

Enthalpy

Enthalpy of a pure substance is given by the sum of internal energy and pv work. Thus enthalpy is
expressed as,

h = u +pv

and change in enthalpy

Δh12 = h2-h1

= (u2 –u1) + (p2 v2 – p1 v1)

= Δu12 + 1w2

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Two-property rule
Two property rule states that "The state of a pure substance of given mass can be fixed by specifying
two properties provided that the system is in equilibrium with negligible effects of gravity, motion,
electricity, magnetism and capilarity".

The two property rule can be applied to both liquids and gases. Since solids can have different
pressures according to direction of measurement, the rule cannot be applied to them. Solids
however require more than two properties to specify the state of a system. The two property rule is
obeyed by some substances which are not pure.

lf a, b and c are the three properties of a system, then two property role can be symbolically
represented by,

c =f (a,b)

where f() means some function of c.

Let p, v and T be the pressure, specific volume and temperature for a specific substance considered
respectively

By using two property rule we can write,

pv =(A+BT)

where A and B are constants.

Specific heat at constant volume

The specific heat at constant volume is defined as the rate of change of internal energy of the
system with respect to temperature when specific volume is held constant Symbolically,

For a closed system comprising of a unit mass of pure substance from first law of thermodynamics,
we have,

q = w + Δu

In differential form,

δq =du + δw

Assuming only displacement work,

δq =du +p.δw

lf the volume is constant then heat transferred becomes equal to change in internal energy

q = (Δu)v

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Integrating between limits

Specific heat constant pressure

The specific beat at constant pressure is defined as the rate o, change of specific enthalpy of the
system with respect to temperature when the pressure is held constant.

Symbolically

For a closed system comprising of a unit mass of pure substance, from first law of thermodynamics,

If the pressure is held constant then heat transferred becomes equal to change in enthalpy

Integrating between the limits

Steady state-steady flow energy equation and its important applications

Consider the flow of fluid in a control volume as shown in figure 3.10. During a small time .interval dt
both mass and energy flow into and out of the control volume at sections 1-1 and 2-2 respectively

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Applications

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Steady flow energy equation is very useful for analysing, work developing systems, work absorbing
systems and neither work developing nor work absorbing systems.

Work Absorbing systems

1.Rotary compressor

Rotary compressors are employed where high efficiency, medium pressure rise upto 10 bar and
large flow rates upto 50 m)/s are required.

In a rotary compressor,

• Work is done on the system to compress the fluid. Hence W2 is negative.

• Potential energy change is negligible.

• Heat is lost by the system for cooling water and hence Q is negative.

Applying steady flow energy equation,

Ignoring K.E. and assuming adiabatic flow due to high flow rates,

2. Reciprocating compressor

A reciprocating compressor is used to increase the pressure of the fluid as high as 1000 bar and to
deliver a small quantity of the fluid (about 5 m3/s). It has a piston cylinder arrangement to compress
the fluid and a receiver to ensure uniform flow rate in the control volume. In a reciprocating
compressor

• Potential and kinetic energies are ignored.

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• Work is done on the system to compress the fluid. Hence,W2 is negative.

• Heat is lost to the system. Hence, Q2 is negative.

Applying steady state energy equation.

3. Centrifugal pump

A pump is a device used to convert mechanical energy into potential energy of liquid using rotating
wheels called rotors. In a centrifugal pump,

• Work is done on the system which is considered as negative.

• Heat transfer is zero.

• Change in internal energy is zero due to no change in temperature of water

Applying steady flow energy equation,

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Work developing systems

Examples of work developing system are, steam or water turbines, reciprocating engines namely IC
engines and steam engines, etc.

1. Steam or Gas Turbine

A turbine is a device used to generate power using the fluid which expands from high pressure to
low pressure. In a steam or gas turbine,

• Work is done by the system and hence W2 is +ve.

• Change in kinetic energy is negligible.

• Heat transfer is negligible due to insulation of walls

Applying steady flow energy equation.

2. Hydraulic Turbine

It is a prime mover which uses potential and kinetic energy of water to move the. Runner of the
turbine. The mechanical energy thus generated can be used to run a generator to produce' power.

In a hydraulic turbine,

 Work is done by the system and it; considered as positive.

 Heat transfer is negligible.
 Change in temperature of water is zero and subsequently change in internal.energy.is
neglected.

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Applying steady flow energy equation,

Non work absorbing and Non work developing systems

Examples of non-work absorbing and non-work developing systems are, evaporators, boilers, all
types of heat exchangers etc.

1. Heat exchanger (Condenser)

A heat exchanger is a device in which heat is transferred from one fluid to another fluid. A steam
condenser is a type of heat exchanger in which steam, after expansion in the turbine condenses by
exchanging heat with cold water flowing through the tubes. Thus, condenser uses both water and
steam as steady flow fluids.

In a condenser (heat exchanger)

• No work is done and therefore, W2 = 0

• No heat transfer due to perfect insulation.

• No change in kinetic and potential energies.

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If mw and ms are the mass of water and mass of steam, hs and hr are enthalpy of steam and
condensate and hwis the enthalpy of water,

then Heat lost by steam = Heat gained by water

2. Evaporator

An evaporator extracts heat from the cooling cabinet of a refrigeration system. The refrigerating
liquid enters the evaporator and absorbs latent heat from the cooling cabinet and leaves the cabinet
in the form of a vapour, at constant pressure.

In an evaporator,

• No work is done and therefore, W2 = 0 .

• No change in kinetic and potential energy.

Applying steady flow energy equation,

Second Law of Thermodynamics:

Thermal Reservoir
A thermal energy reservoir (TER) is a large body of i;lfinite heat capacity, capable of absorbing or
rejecting heat of unlimited quantity without undergoing any appreciable changes in its
thermodynamic coordinates. Any changes that take place due to heat interaction may be very slow
and very minute so that all the process in a TER can be regarded as quasi-static. Consider a cyclic
heat engine (CHE) as shown in fig. 4.2

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With reference to the above figure, the thermal energy reservoir (TER)H from which Q1 quantity of
heat is transferred to the system operating in a heat engine cycle is called source. Similarly, the
thermal energy reservoir (TER)L to which Q2 quantity of heat is rejected is called sink.

A mechanical energy reservoir (MER) is a large body essentially enclosed by an adiabatic

impermeable wall capable of storing work either as potential energy or as kinetic energy. All the
processes in a MER are essentially quasi-static.

Concepts of Heat Engine, Heat Pump, coefficients of performance.

HEAT ENGINE

A heat engine may be defined as a system operating in a cycle and producing useful work by
abstracting heat from a suitable heat source. Consider a heat engine that receives Q1 amount of heat
from a high temperature source at Tr Some of the heat thus received is utilized to do mechanical
work W. The engine rejects Q2 amount of heat to a low temperature sink at T2

Applying the first law to the heat engine,

or Net heat transfer = Net work transfer

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Generally the performance of the heat engine is expressed in efficiency of the engine. Thus thermal
efficiency of heat engine

Thus, in order to increase the thermal efficiency of the heat engine we have to reduce the heat
rejected to the sink Q2 or we have to increase the heat supplied to the engine Q1

Reversible heat engines,

In reversed heat engines the direction of flow of heat and work are exactly opposite. These
machines are used to remove heat from a body kept at a lower temperature and to transfer this
heat to a body at a higher temperature. Examples of reversed heat engines are refrigerator and heat
pump.

Refrigerator

A refrigerator is a device which working in a cycle delivers heat from low temperature region to a
high temperature region. The purpose of refrigerator is to cool the space by absorbing heat from it
and to maintain this space at a temperature lower than that of the surroundings. Refrigerators are
used to preserve food items and drugs at low temperature.

The performance of a refrigerator is expressed in terms of COP or coefficient of performance

COP of refrigerator,

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Heat Pump

A heat pump is a device which working in a cycle delivers heat from low temperature region to a
high temperature region. The purpose of the heat pump is to take the heat from low temperature
space and supply it to a high temperature sink for heating. Heat pumps are useful to keep the rooms
warm in winter season.

The efficiency of heat pump is expressed in terms of COP. Thus,

Kelvin – Planck statement of the Second law of Thermodynamics;

"It is impossible to construct an engine which operating in a cycle, will produce no other effect
than the extraction of heat from a single heat reservoir and performs an equivalent amount of
work".

The above statement is known as Kelvin-Planck Statement of second law of thermodynamics. Thus,
according to the statement one cannot develop a heat engine that receives Q amount of heat from a

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high temperature source and does an equivalent amount of work W. The efficiency of such engine
would be W/Q = 100%. Such an engine even though satisfies principle of conservation of energy, it
violates Kelvin-Planck statement.

Thus a heat engine can receive Q1 amount of heat from a high temperature source, a part of it is
utilized to do work W before Q2 amount of heat is rejected to the low temperature sink as shown in
figure 4.5 (b).

Claussius statement of second law of Thermodynamics

"It is impossible to construct an engine which operating in a cycle, transfers heat from a body at a
lower temperature to a body at a higher temperature without the assistance of external work".

OR

"It is impossible for heat energy to flow from a lower temperature body to a higher temperature
body without the assistance of external work ".

The above statement is known as Clausius Statement of second law of thermodynamics. Thus,
Clausius statement makes it clear that heat cannot flow itself from a low temperature region to a
high temperature region without the assistance of an external work.

Equivalence of Kelvin Planck and Clausius statements

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Consider a high temperature reservoir (source) at T1 and a low temperature reservoir (sink) at T2 as
shown in Figure 4.7

Consider figure 4.7 (a). In this case a heat pump HP operates in a cycle and transfers Q1 amount of
heat from a low temperature sink to a high temperature source without any work input. This system
violates Clausius statement.

Consider figure 4.7 (b). In this case, a heat engine HE operates in a cycle absorbing Q1 amount of
heat from a high temperature source. The engine does W amount of work and finally rejects Q2
amount of heat to the low temperature sink. This system operates as per Kelvin Planck Statement.

Consider figure 4.7 (c). In this case both the heat pump and the heat engine are combined together
to form a combined system. This system constitutes a device that receives (Q1 – Q2) amount of heat
from the high temperature source and does an equivalent amount of work W = Q1 – Q2 Hence this
system violates Kelvin Planck Statement.

Thus, violation of Clausius statement leads to violation of Kelvin-Planck statement.

Consider a high temperature reservoir (source) at T1 and a low temperature reservoir (sink) at Tl as
shown in figure 4.8.

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Consider figure 4.8 (a). In this case a heat engine extracts Q1 amount of heat from a high
temperature source and does an equivalent amount of work W = Q1 without rejecting heat to the
low temperature sink. This system violates Kelvin Planck Statement.

Consider figure 4.8 (b). In this case, a heat pump working in a cycle, extracts Q1 amount of heat from
a low temperature sink. The heat pump also receives W = Q1 amount of work from an external
source and supplies (Q1 + Q2) amount of heat to the high temperature source.This system works as
per Clausius Statement.

Consider figure 4.8 (c). In this case, both the heat engine and the heat pump are clubbed together to
form a combined system. Since the output of the engine W is used to drive the heat pump, input to
the combined system is only from the Q2 amount of heat extracted from the low temperature sink.
The system rejects same amount of heat to the high temperature source without any external work
input. This system .violates Clausius statement.

Thus, violation of Kelvin-Planck statement leads to violation of Clausius statement.

Hence we can conclude that both Kelvin-Planck and Clausius statements are equivalent in sense.

Preputial motion machine of first kind

A perpetual motion machine of the first kind is an engine working in a cycle without receiving heat
from any source, but delivering work to the surroundings.

From the first law of thermodynamics, we have

Thus, if the cycle heat input ∮ δQ is zero, it is possible to obtain useful work ∮ δW. Hence perpetual
motion machine of first kind is impossible.

Preputial motion machine of second kind

A perpetual motion machine of second kind (PMM - If) is an engine working in a cycle developing net
work by exchanging heat from a single heat source. Such an engine shown in figure 4.9 is impossible
as per Kelvin-Planck statement. If such an engine were possible, it should extract .heat from an
infinite heat low temperature reservoir and deliver an equivalent amount of work to the
surroundings. Instead of receiving heat directly from a low temperature reservoir, if the PMM - II
receives heat from a high temperature reservoir, it is possible to do work.

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Thermal efficiency of a practical heat engine exchanging heat between two thermal reservoirs is
given by

Such an engine (PMM - In violates Kelvin-Planck statement of II law

Carnot cycle, Carnot principles.

The Carnot cycle can be applied to a non-flow process with the following requirements.

 A working fluid, generally a perfect gas

 A frictionless piston sliding in a perfectly sealed cylinder. Both piston and cylinder are
perfectly insulated.
 A perfectly conducting cylinder head.
 A hot source or a heat reservoir of infinite capacity at the maximum temperature T1 = Tmax
 A cold sink or a heat reservoir of infinite capacity at the minimum temperature T2 = Tmin
 All processes are reversible processes and are performed at an infinite slow pace.

As shown in the figure 4.20 on thep- V and T-s diagrams, the cycle consists of four reversible
processes.

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Thermodynamic temperature scale,
Any property which depends solely on temperature can be used to define a temperature scale. The
thermodynamic temperature scale is the one which doesn't depend on the properties of any
particular substance.

Let θ denote temperature measured on any scale and let the source and sink temperature between
which a reversible engine works be 𝜃 , and 𝜃 , as shown in Fig. 4.23

The efficiency of this reversible engine, which is independent of the working fluid is a function of
temperature only. If Q1, and Q2 are respectively the heat quantities received from the source at 𝜃
and rejected to the sink and 8z then engine efficiency is given by

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The above expression (5) forms the basis of a thermodynamic temperature scale suggested by Lord
Kelvin. If one of the two temperatures is fixed and assigned a number, the other temperature can be
determined. At present this fixed point or reference temperature is taken as triple point
temperature of water which is assigned a numerical value of 273.16 K.

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 Consider a Carnot engine operating between two thermal reservoirs kept at temperatures T and Ttp
respectively, Then we can write

In the above equation if Q = 0, then T = 0. Thus the thermodynamic temperature scale presents the
idea of absolute zero temperature.

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