Module III

Applications of laws thermodynamics

Principles of fluid flow:-

Continuity equation
Law of conservation of mass is given by
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑎𝑐𝑐𝑢𝑚𝑢𝑎𝑙𝑡𝑖𝑜𝑛 𝑜𝑓 𝑚𝑎𝑠𝑠 𝑁𝑒𝑡 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑚𝑎𝑠𝑠 𝑜𝑢𝑡
( )+( )=0
𝑤𝑖𝑡ℎ 𝑖𝑛 𝑡ℎ𝑒 𝑐𝑜𝑛𝑡𝑟𝑜𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑏𝑦 𝑡ℎ𝑒 𝑓𝑙𝑜𝑤𝑖𝑛𝑔 𝑠𝑡𝑟𝑒𝑎𝑚.
Mathematically
𝑑𝑚
+ ∆(𝜌𝑢𝐴) = 0
𝑑𝑡
For steady state
∆(𝜌𝑢𝐴) = 0
𝜌1 𝑢1 𝐴1 = 𝜌2 𝑢2 𝐴2
Energy equation:
Law of conservation of energy is given by
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑎𝑐𝑐𝑢𝑚𝑢𝑎𝑙𝑡𝑖𝑜𝑛 𝑜𝑓 𝑒𝑛𝑒𝑟𝑔𝑦 𝑁𝑒𝑡 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑢𝑡
( )+( )=𝑄−𝑊
𝑤𝑖𝑡ℎ 𝑖𝑛 𝑡ℎ𝑒 𝑐𝑜𝑛𝑡𝑟𝑜𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑏𝑦 𝑡ℎ𝑒 𝑓𝑙𝑜𝑤𝑖𝑛𝑔 𝑠𝑡𝑟𝑒𝑎𝑚.
Mathematically,
𝑑𝑈
+ ∆(𝐾. 𝐸) + ∆(𝑃. 𝐸) + ∆(𝑈) + ∆(𝑃𝑉) = 𝑄 − 𝑊
𝑑𝑡
For steady state
𝑢2
∆ ( + 𝑔𝑧 + 𝐻) = 𝑄 − 𝑊
2

Flow through Nozzles

A nozzle is a device for converting thermal energy or mechanical energy in to kinetic energy.
This is achieved by changing cross sectional area. It finds application in turbines, ejectors,
diffusers etc…
Mach Number (M):
It is the ratio of velocity of the object to the velocity of sound. Denoted by M
𝑣
𝑀=
𝑐

V- velocity of object
c- velocity of sound

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Based on Mach number the flow is classified as
Subsonic: M<1 , c>v
Sonic: M=1 , v=c
Super sonic, M>1 v>c
Hyper sonic: M>>1 v>>c
If M<<1 the fluid is incompressible for M<0.3
Nozzle are mainly of three types
Convergent
Divergent
Convergent divergent

Velocity at throat

𝑢𝑡ℎ𝑟𝑜𝑎𝑡 = √𝛾𝑃𝑉

Throttling process (Joule-Thomson Expansion)

Throttling process, also known as Joule—Thomson expansion, is a steady-state steady-flow
process across a restriction, which results in a reduction in pressure for the fluid. The flow
through a partially opened valve or a porous plug is a typical example of throttling process.

The throttling process may be treated as an adiabatic operation, because the expansion takes
place in a very short time within a very small region, so that he heat exchange between the
system and the surroundings is negligible. As no mechanisms are present for extracting work,
the process is a highly irreversible one.

Joule—Thomson expansion is an isenthalpic process. The temperature of the gas changes as

a result of this expansion. The change in temperature resulting from the throttling operation is
known as the Joule—Thomson coefficient μ, which is defined as

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 𝜕𝑇
𝜇=( )
𝜕𝑃 𝐻

During expansion ∆P is negative. Therefore, a positive value of Joule—Thomson coefficient

means that ∆T is negative and the gas cools on throttling. On the other hand, a negative
Joule—Thomson coefficient means that throttling results in an increase in temperature.
Joule—Thomson coefficient of a gas can be determined using the pressure volume
temperature relationship.

REFRIGERATION
Refrigeration is the process of producing and maintaining a temperature below that of the
surrounding atmosphere. Refrigeration processes find wide applications in chemical process
industries.
Applications:

• In manufacturing synthetic rubber, textiles, chlorine, plastics, hydrogen fluoride, etc.

• To remove heat of chemical reactions and to liquefy process gases for gas separation
by distillation and condensation.
• Liquefaction processes for the production of pure gases such as oxygen and nitrogen
from air and liquefaction and storage of natural gases employ refrigeration principles.
• Separation of volatile hydrocarbons in petroleum industries, separation of gasoline
from natural gas, solvent recovery
• Crystallisation of salts from solutions,
• manufacture of ice, treatment, transport and preservation of food and beverages, etc.,
are some
• air-conditioning of houses and buildings and in domestic refrigerators, and in large
scale plants
Refrigeration implies production of low temperature by continually absorbing heat at a low
level and rejecting it at a high level. Since heat cannot flow from a body at low temperature
to one at a higher temperature spontaneously, external work is required to achieve
refrigeration. Thus, refrigeration is essentially an operation involving the pumping of heat
from one temperature to a higher temperature. In mechanical refrigeration, which is the most
commonly used method for commercial applications, the low temperature is produced by the
evaporation of a liquid whose properties are, such that, at the pressure of evaporation, the
saturation temperature is low. The evaporated liquid is then returned to its original state for
continuous operation. The complete series of processes that the working fluid undergoes
constitute a refrigeration cycle. The working fluid used is called refrigerant.

A typical refrigeration cycle includes

• Evaporation of the liquid refrigerant
• Compression of the refrigerant vapour
• Condensation of the vapour into liquid
• Finally expansion of the liquid.

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Coefficient of performance:
The efficiency or coefficient of performance (COP) of a refrigerator is defined as the quantity
of heat absorbed at the low temperature per unit of work.
𝑄2 𝑄2
𝐶𝑂𝑃 = =
𝑊 𝑄1 − 𝑄2

Refrigerator capacity
The capacity is sometimes measured in ton of refrigeration. One ton is defined as the heat
absorption at the rate of 12000 BTU per hour
(One BTU is the amount of heat required to raise the temperature of one pound, i.e. 0.4536
kg of water by one degree Fahrenheit or (1/1.8) K. Thus, 1 BTU = 1.055kJ).

This rate corresponds to the rate of heat removal that is required to freeze 1 ton of water in a
day originally at 273 K. One ton of refrigeration is equivalent to a refrigeration rate of 12660
kJ/h in SI units.

Carnot cycle
The Carnot cycle can be used as a model of the ideal refrigeration cycle, because, of all the
refrigerators operating between the same two thermal reservoirs, the maximum COP is
attained by the one based on Carnot cycle.

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It consist of the following steps:
• Reversible adiabatic compression (AB),
• isothermal heat rejection(BC)
• reversible adiabatic expansion (CD)
• and isothermal heat absorption (DA).
During the isothermal heal absorption (DA) on amount of heat Q2 is absorbed at low
temperature level T2. The area ADXY lie T-S diagram represent the heat absorbed. It is equal
to T2∆S, where ∆S is the change in entropy of the fluid due to the heat absorption. Heat
rejected at higher temperature T1 is equal to Q1 and is represented by the area BCXY. It is
equal to T1∆S. The external work done for this transfer of bent against a temperature gradient
is given by W = Q1-Q2, which is the enclosed area ABCD

The coefficient of performance of the Carnot cycle is,

𝑄2 𝑄2 𝑇2
𝐶𝑂𝑃 = = =
𝑊 𝑄1 − 𝑄2 𝑇1 − 𝑇2
Vapour compression refrigeration cycle
The actual refrigeration cycles are less efficient than the ideal Carnot cycle, because of
presence of the inevitable irreversible effects, such as friction, imperfect heat insulation,

In the vapour-compression cycle shown in figure.

• The refrigerant vapour is compressed (AB) to such a pressure that the available
Coolingwater can condense the vapour.
• In a condenser (BC) operated at this pressure which is maintained constant. The
vapour, during condensation rejects heat to the cooling medium.
• By passing through a throttling valve, the pressure of the liquid leaving the condenser
is reduced (CD) to thepressure maintained in the evaporator.
• The liquid then evaporates (DA), absorbing heat at constant temperature T2.

The vapour thus produced enters the compressor, and the cycle is repeated.

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It is possible that the vapour leaving the refrigerator may get slightly superheated or may be
slightly unsaturated.

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Choice of refrigerant

The commonly used refrigerants are the halogenated hydrocarbons such as Freon-12 find
wide application. They have the advantages that they are non- toxic, non-flammable, and
non-explosive. Methyl chloride, carbon dioxide, sulphur dioxide, propane, and ammonia are
other commonly used refrigerants. The important properties of a refrigerant are as follows.

1. Boiling temperature. It is necessary that the operating pressure be maintained above

atmospheric to avoid air and moisture leaks into the system. The normal boiling point
of the refrigerant should, therefore, be lower than the desired temperature levels in the
refrigerator.
2. Freezing point: The freezing point of the refrigerant should be well below the
minimum temperature at which the system is operated.
3. Critical temperature and pressure: The critical temperature and pressure of the
refrigerant should be above the operating system temperature and pressure. If the
operating temperature is above the critical temperature, it is impossible to condense
the gas by compressing it to high pressures.

4. Condenser and evaporator pressure: The condenser pressure should not be very high.
If the pressure is very high the cost of equipment and the cost of operation would be
excessive if the evaporator pressure is excessively low, the compression ratio will be
very high Very high

5. Specific volume: specific volume of the vapour determines the size of the compressor
low suction volume are desirable for reciprocating compressors and high suction
volumes for centrifugal compressors

6. Latent heat: high latent heat of vaporisation of the refrigerant is desirable. Because it
results in high refrigerating effect per unit weight of the refrigerant.

7. Specific heat: low specific heat is preferred. As its less heat of removal.

8. Molecular weight : high molecular weight refrigerant gives high specific volume
preferred in centrifugal compressors and low molecular weight in reciprocating
compressors.

9. Safety aspects: non-flammable, non toxic, non explosive

10. Other desirable properties: long life, non corrosive, low viscosity , high thermal
conductivity.

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 STEAM POWER PLANTS

Steam-power plants operate on a closed cycle.

Rankine Cycle:

The components of a Rankine cycle, also known as the standard vapour-power cycle.

• Water at low temperature and pressure is compressed isentropically to the boiler

pressure by the feed pump (1—2).
• In the boiler, heat is supplied to the water at constant pressure, whereby, its
temperature rises to the saturation temperature corresponding to the pressure in the
boiler. Further supply of heat results in the evaporation of water and in superheating
the vapour, thus produced (2—3).
• The superheated vapour at the elevated pressure is then allowed to expand
isentropically in a turbine to the condenser pressure (3—4).
• In the condenser, the low-pressure exhaust steam from the turbine gives out its heat to
the cooling water at constant pressure (4—1).
The saturated liquid water leaving the condenser then enters the feed pump and the cycle is
repeated.

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 INTERNAL COMBUSTION ENGINE
The steam power plants and internal combustion engines are broadly designated as heat
engines. because in both, the chemical energy of a fuel is converted into heat energy, which is
utilised to perform mechanical work, internal combustion engine differs from steam power
plants such that the former operates on open cycles whereas the latter on closed cycles. In
internal combustion engines, the working fluid which is a mixture of air and fuel is burned
inside the engine and after a series of processes which results in the production of mechanical
work, the combustion products are discarded. The working fluid does not undergo a cycle of
changes in an internal combustion engine, as does the steam in a steam power plant.
However, the engine operates on a closed mechanical cycle. The internal combustion engines
involve no transfer of heat through surfaces, which restrict the temperature and pressure, as is
the case with the boiler of the steam power plants.

The high temperatures and the absence of heat transfer surfaces are the main advantages of
internal combustion engines over steam power generation systems.

The thermodynamic analysis of internal combustion engine is made possible by devising

ideal closed cycles with air as the working fluid and by comparing the performance of actual
cycles with these ideal air-standard cycles. The assumptions involved in this approach are:

1. The working fluid is a fixed mass of air and it undergoes no chemical change. Air is
assumed to behave as an ideal gas.
2. The combustion process in the actual cycle is replaced by a heat transfer process in
the ideal cycle. Heat is assumed to be transferred from an external heat source.
3. The exhaust stroke ¡n the actual engine is replaced by a heat rejection step in the ideal
cycle. Heat is assumed to be transferred to the surroundings.
4. The air is assumed to have constant specific heat and all the processes are internally
reversible.

The Otto cycle and the Diesel cycle are the two important air-standard cycles used for
analysis of internal combustion engines,

Otto Cycle

The P-V and T-S diagram of the air-standard Otto cycle are shown. The cycle is characterised
by the following processes:

1. Process 1—2: A given mass of air, assumed an ideal gas, is compressed isentropical,
during the inward stroke of the piston. As a result, the temperature of the gas
increases from T1 toT2.
2. Process 2—3: 1-Heat (Q1) is supplied to the system at Constant volume by allowing
the system to come in contact with a high-temperature reservoir. The heat transfer
results in the increase in temperature from T2 to T3. It also increases the pressure and
entropy of the fIuid (In actual engines, this process is achieved approximately by
igniting the compressed gas by means of a spark. The combustion of the fuel/air
mixture occurs so rapidly that it may be by a constant volume process).
3. Process 3—4: The air is expanded isentropically during the outward stroke of the
[Link] the pressure and temperature decrease during this process. Temperature

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 decreases from T3 to T4 during this step. (In actual engines, the products of
combustion at very high pressure and temperature expand approximately adiabatically
during this step.)
4. Process 4—I: Heat (Q2) is transferred from the system reversibly, at constant volume
to a low-temperature reservoir. The temperature, pressure, and entropy of the system
decrease during this stage. (In actual engine, during the corresponding process the
exhaust valve opens and the pressure falls rapidly at nearly constant volume.)

Diesel cycle :
The P-V and T-S diagram of the air-standard Diesel cycle are shown in Fig. The Diesel
engines differ from the Otto engines, in so far as in the former, the temperature at the end of
compression exceeds the fuel ignition temperature and the combustion of fuel occur
spontaneously.

The Diesel cycle consists of the following processes

1. Process 1—2: Air assumed to behave as an ideal gas, is compressed isentropically to a

high temperature and pressure. The temperature of the gas increases from T1 to T2.
2. Process 2—3: Heat Q1 is supplied to the fluid at constant pressure. The temperature
increases to T3. (In actual engines, this is accomplished by injecting the fuel to the hot
compressed air at the end of the compression stroke. The fuel ignites spontaneously
and the piston starts moving outward slowly.)
3. Process 3—4 : The gas undergoes an isentropic expansion by which the pressure and
temperature of the gas decreases. The temperature attained after expansion process is
T4

4. Process 4—1: Heat Q2 is rejected at constant volume thus decreasing the temperature
and pressure of the gas further. (In actual engines, during the corresponding stage, the
discharge port opens and the combustion products are exhausted. )

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Thermodynamic properties of fluid

Thermodynamic properties of fluid can be classified in to three broad group

1. The reference properties
2. The energy properties
3. The derived properties
Reference properties

Reference properties are also as primary properties. These properties are the ones that are
used to define the state of the system. They have absolute values, as against energy
properties, which are measured relative to some arbitrary reference state. Examples of
reference properties are temperature, pressure, volume, and entropy. Of these, temperature
and pressure are intensive, and volume and entropy are extensive. In addition to these, in
dealing with the solutions, the composition is also treated as a reference property.

Energy Properties

The four energy properties are the internal energy (U), enthalpy (H), the Helmholtz free energy
(A), and the Gibbs free energy (G). All are extensive thermodynamic properties and are known
relative to some reference state. These are referred to as energy properties, because, the changes
in these thermodynamic functions indicate useful work under certain conditions of restraint.

Derived properties

These are partial derivatives of energy properties or the reference properties. Examples
include specific heat, coefficient of expansion, Joule-Thomson coefficient and coefficient of
compressibility

WORK FUNCTION (HELMHOLTZ FREE ENERGY)

The Helmholtz free energy (A) of a system is defined as

𝐴 = 𝑈 − 𝑇𝑆

where U, T, and S are the internal energy, temperature, and entropy of the system
respectively. Since U, T, and S are characteristic of the system and depend only on its
thermodynamic state. Helmholtz free energy is a state function. Since U and S are both
extensive, A is also an extensive property.

To understand the physical significance of the work function, consider an isothermal

reversible change occurring from state 1 to state 2. Then from Eq. (6.1), the change in the
work function accompanying this process is

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 ∆𝐴 = ∆𝑈 − 𝑇∆𝑆
∆𝐴 = ∆𝑈 − 𝑄𝑅
∆𝑈 = 𝑄𝑅 − 𝑊𝑅

∆𝐴 = −𝑊𝑅
The decrease in the work function accompanying a process at constant temperature is equal to
the reversible work done by the system during the process.

GIBBS FREE ENERGY

Gibbs free energy is given by

G=H-TS

The Gibbs Free Energy represent the decrease in the maximum useful work rather than the
reversible work . Like the work function A, Gibbs free energy G is a single valued function
of the thermodynamic state of the system and is an extensive property. It is widely used in the
study of phase equilibria and chemical reaction equilibria.
The physical significance of the Gibbs free energy function can be made clear if we consider
a reversible process at constant temperature and pressure.
∆𝐺 = ∆𝐻 − 𝑇∆𝑆
∆𝐺 = ∆𝑈 + 𝑃∆𝑉 − 𝑇∆𝑆
∆𝐺 = ∆𝐴 + 𝑃∆𝑉
∆𝐺 = −𝑊𝑅 + 𝑃∆𝑉

6.6 FUGACITY

The concept of fugacity was introduced by G N Lewis and is widely used in solution
thermodynamics to represent the behavior of real gases. The name fugacity is derived from
the Latin word for ‘fleetness' or the escaping tendency. It has been widely used in the study
of phase and chemical reaction equilibria involving gases at high pressure

The fugacity is related to Gibbs free energy by

𝑑𝐺 = 𝑅𝑇𝑑(𝑙𝑛𝑓)

CHEMICAL POTENTIAL

The chemical potential, denoted by the symbol µ, is a widely used thermodynamic property.
It is used as an index of chemical equilibrium in the same manner as temperature and
pressure are used as indices of thermal and mechanical equilibrium. The chemical potential µi
of component i in a solution is the same as its partial molar free energy in the solution, G.
That is, chemical potential of a component i in a solution can be defined as
𝜕𝐺
𝜇𝑖 = 𝐺̅𝑖 = ( )
𝜕𝑛𝑖 𝑇,𝑃,𝑛

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