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# Principles of Thermodynamics:

The laws of thermodynamics, in principle, describe the specifics for the transport of heat and
work in thermodynamic processes. Since their inception, however, these laws have become some
of the most important in all of physics and other types of science associated with
thermodynamics.It is wise to distinguish classical thermodynamics, which is focused on systems
in thermodynamic equilibrium, from non-equilibrium thermodynamics. The present article is
focused on classical or thermodynamic equilibrium thermodynamics.
There are generally considered to be four principles (referred to as "laws"):
1. The zeroth law of thermodynamics, which underlies the definition of temperature.
2. The first law of thermodynamics, which mandates conservation of energy, and states in
particular that heat is a form of energy.
3. The second law of thermodynamics, which states that the entropy of an isolated
macroscopic system never decreases, or (equivalently) that perpetual motion machines
are impossible.
4. The third law of thermodynamics, which concerns the entropy of a perfect crystal at
absolute zero temperature, and implies that it is impossible to cool a system all the way to
exactly absolute zero.

## Zeroth law of thermodynamics

If two thermodynamic systems are each in thermal equilibrium with a third, then they are in
thermal equilibrium with each other.

When two systems are put in contact with each other, there will be a net exchange of energy
between them unless or until they are in thermal equilibrium, that is, they are at the same
temperature. While this is a fundamental concept of thermodynamics, the need to state it
explicitly was not perceived until the first third of the 20th century, long after the first three
principles were already widely in use, hence the zero numbering. The Zeroth Law asserts that
thermal equilibrium, viewed as a binary relation, is a transitive relation (and since any system
is always in equilibrium with itself, it is furthermore an equivalence relation).

## First law of thermodynamics

Energy can neither be created nor destroyed. It can only change forms.
In any process in an isolated system, the total energy remains the same.
For a thermodynamic cycle the net heat supplied to the system equals the net work done by the system.

The First Law states that energy cannot be created or destroyed; rather, the amount of energy
lost in a steady state process cannot be greater than the amount of energy gained. This is the

statement of conservation of energy for a thermodynamic system. It refers to the two ways that
a closed system transfers energy to and from its surroundings by the process of heating (or
cooling) and the process of mechanical work. The rate of gain or loss in the stored energy of a
system is determined by the rates of these two processes. In open systems, the flow of matter is
another energy transfer mechanism, and extra terms must be included in the expression of the
first law.
The First Law clarifies the nature of energy. It is a stored quantity which is independent of any
particular process path, i.e., it is independent of the system history. If a system undergoes a
thermodynamic cycle, whether it becomes warmer, cooler, larger, or smaller, then it will have
the same amount of energy each time it returns to a particular state. Mathematically speaking,
energy is a state function and infinitesimal changes in the energy are exact differentials.
All laws of thermodynamics but the First are statistical and simply describe the tendencies of
macroscopic systems. For microscopic systems with few particles, the variations in the
parameters become larger than the parameters themselves, and the assumptions of
thermodynamics become meaningless. The First Law, i.e. the law of conservation, has become
the most secure of all basic principles of science. At present, it is unquestioned (although it is
said to be criticized by people who do not accept the idea that the potential to gain energy is a
form of actual energy).
Fundamental Thermodynamic Relation:
The first law can be expressed as the Fundamental Thermodynamic Relation:
Heat supplied = internal energy + work done

## Here, E is internal energy, T is temperature, S is entropy, p is pressure, and V is volume. This is

a statement of conservation of energy: The net change in internal energy (dE) equals the heat
energy that flows in (TdS), minus the energy that flows out via the system performing work
(pdV).

## Second law of thermodynamics

The entropy of an isolated system consisting of two regions of space, isolated from one another, each in
thermodynamic equilibrium in itself, but not in equilibrium with each other, will, when the isolation that
separates the two regions is broken, so that the two regions become able to exchange matter or energy,
tend to increase over time, approaching a maximum value when the jointly communicating system
reaches thermodynamic equilibrium.

In a simple manner, the second law states "energy systems have a tendency to increase their
entropy rather than decrease it." This can also be stated as "heat can spontaneously flow from a

higher-temperature region to a lower-temperature region, but not the other way around." (Heat
can flow from cold to hot, but not spontaneously- for example, when a refrigerator expends
electrical power.)
A way of thinking about the second law for non-scientists is to consider entropy as a measure of
ignorance of the microscopic details of the system. So, for example, one has less knowledge
about the separate fragments of a broken cup than about an intact one, because when the
fragments are separated, one does not know exactly whether they will fit together again, or
whether perhaps there is a missing shard. Solid crystals, the most regularly structured form of
matter, have very low entropy values; and gases, which are very disorganized, have high entropy
values. This is because the positions of the crystal atoms are more predictable than are those of
the gas atoms.
The entropy of an isolated macroscopic system never decreases. However, a microscopic system
may exhibit fluctuations of entropy opposite to that stated by the Second Law (see Maxwell's
demon and Fluctuation Theorem).

## Third law of thermodynamics

As temperature approaches absolute zero, the entropy of a system approaches a constant minimum.

Briefly, this postulates that entropy is temperature dependent and results in the formulation of the
idea of absolute zero.

Topping cycle:
In a topping cycle, the fuel supplied is used to first produce power and then thermal energy,
which is the by-product of the cycle and is used to satisfy process heat or other thermal
requirements. Topping cycle cogeneration is widely used and is the most popular method of
cogeneration.
The four types of topping cycle cogeneration systems are briefly explained in Table

## 1.A gas turbine or diesel

engine producing electrical or
mechanical power followed
by a heat recovery boiler to
create steam to drive a
secondary steam turbine. This
is called a combined-cycle
topping system.

## 2.The second type of system

burns fuel (any type) to
produce high-pressure steam
that then passes through a
steam turbine to produce
power with the exhaust
provides low-pressure process
steam. This is a steam-turbine
topping system.

## 3.A third type employs heat

recovery from an engine
exhaust and/or jacket cooling
system flowing to a heat
recovery boiler, where it is
converted to process steam /
hot water for further use.

## 4.The fourth type is a gasturbine topping system. A

natural gas turbine drives a
generator. The exhaust gas
goes to a heat recovery boiler
that makes process steam and
process heat

Bottoming cycle:
In a bottoming cycle, the primary fuel produces high temperature thermal energy and the heat
rejected from the process is used to generate power through a recovery boiler and a turbine
generator. Bottoming cycles are suitable for manufacturing processes that require heat at high
temperature in furnaces and kilns, and reject heat at significantly high temperatures. Typical
areas of application include cement, steel, ceramic, gas and petrochemical industries. Bottoming
cycle plants are much less common than topping cycle plants. The Figure 7.6 illustrates the
bottoming cycle where fuel is burnt in a furnace to produce synthetic rutile. The waste gases
coming out of the furnace is utilized in a boiler to generate steam, which drives the turbine to
produce electricity.

Bottoming cycle:

## ORGANIC RANKINE CYCLE:

The Organic Rankine cycle (ORC) is named for its use of an organic, high molecular mass fluid
with a liquid-vapor phase change, or boiling point, occurring at a lower temperature than the
water-steam phase change . The fluid allows Rankine cycle heat recovery from lower
temperature sources such as industrial waste heat, geothermal heat, solar ponds, etc. The low
temperature heat is converted into useful work, that can itself be converted into electricity. A
prototype was first developed and exhibited in 1961 by Israeli solar engineers Harry Zvi Tabor
and Lucien Bronicki.

## Working principle of the ORC:

The working principle of the organic Rankine cycle is the same as that of the Rankine cycle : the
working fluid is pumped to a boiler where it is evaporated, passes through a turbine and is finally
re-condensed.
In the ideal cycle, the expansion is isentropic and the evaporation and condensation processes are
isobaric.
In the real cycle, the presence of irreversibilities lowers the cycle efficiency. Those
irreversibilities mainly occur :

During the expansion : Only a part of the energy recoverable from the pressure difference
is transformed into useful work. The other part is converted into heat and is lost. The
efficiency of the expander is defined by comparison with an isentropic expansion.

In the heat exchangers : The working fluid takes a long and sinuous path which ensures
good heat exchange but causes pressure drops that lower the amount of power
recoverable from the cycle.

## ORC with Regenerator

In the case of a "dry fluid", the cycle can be improved by the use of a regenerator : Since the
fluid has not reached the two-phase state at the end of the expansion, its temperature at this point
is higher than the condensing temperature. This higher temperature fluid can be used to preheat
the liquid before it enters the evaporator.
A counter-flow heat exchanger is thus installed between the expander outlet and the evaporator
inlet. The power required from the heat source is therefore reduced and the efficiency is
increased.

## Applications for the ORC:

The organic Rankine cycle technology has many possible applications. Among them, the most
widespread and promising fields are the following:

## Waste heat recovery

Waste heat recovery is the most important development field for the ORC. It can be applied to
heat and power plants (for example a small scale cogeneration plant on a domestic water heater),
or to industrial and farming processes such as organic products fermentation, hot exhausts from
ovens or furnaces, flue gas condensation, exhaust gases from vehicles, intercooling of a
compressor, condenser of a power cycle, etc.[1]

## Biomass power plant

Biomass is available all over the world and can be used for the production of electricity on small
to medium size scaled power plants. The problem of high specific investment costs for
machinery such as steam boilers are overcome due to the low working pressures in ORC power
plants. The ORC process also helps to overcome the relatively small amount of input fuel

available in many regions because an efficient ORC power plant is possible for smaller sized
plants.[2]

Geothermal plants

Geothermic heat sources vary in temperature from 50 to 350C. The ORC is therefore perfectly
adapted for this kind of application. However, it is important to keep in mind that for lowtemperature geothermal sources (typically less than 100C), the efficiency is very low and
depends strongly on heat sink temperature (defined by the ambient temperature).

## Solar thermal power

The organic Rankine cycle can be used in the solar parabolic trough technology in place of the
usual steam Rankine cycle. The ORC allows a lower collector temperature, a better collecting
efficiency (reduced ambient losses) and hence the possibility of reducing the size of the solar
field.[3][4][5]
Choice of the working fluid:
The selection of the working fluid is of key importance in low temperature Rankine Cycles.
Because of the low temperature, heat transfer inefficiencies are highly prejudicial. These
inefficiencies depend very strongly on the thermodynamic characteristics of the fluid and on the
operating conditions.
In order to recover low-grade heat, the fluid generally has a lower boiling temperature than
water. Refrigerants and hydrocarbons are the two commonly used components.
Optimal characteristics of the working fluid :

## Isentropic saturation vapor curve :

Since the purpose of the ORC focuses on the recovery of low grade heat power, a superheated
approach like the traditional Rankine cycle is not appropriate. Therefore, a small superheating at
the exhaust of the evaporator will always be preferred, which disadvantages "wet" fluids (that are
in two-phase state at the end of the expansion). In the case of dry fluids, a regenerator should be
used.

## Low freezing point, high stability temperature :

Unlike water, organic fluids usually suffer chemical deteriorations and decomposition at high
temperatures. The maximum hot source temperature is thus limited by the chemical stability of
the working fluid. The freezing point should be lower than the lowest temperature in the cycle.

## High heat of vaporisation and density :

A fluid with a high latent heat and density will absorb more energy from the source in the
evaporator and thus reduce the required flow rate, the size of the facility, and the pump
consumption.

## Low environmental impact

The main parameters taken into account are the Ozone depletion potential (ODP) and the global
warming potential (GWP).

Safety

The fluid should to be non-corrosive, non-flammable, and non-toxic. The ASHRAE safety
classification of refrigerants can be used as an indicator of the fluid dangerousness level.

## Good availability and low cost

Acceptable pressures

## WASTE HEAT RECOVERY:

Introduction:
Waste heat is heat, which is generated in a process by way of fuel combustion or chemical
reaction, and then dumped into the environment even though it could still be reused for some
useful and economic purpose. The essential quality of heat is not the amount but rather its
value. The strategy of how to recover this heat depends in part on the temperature of the waste
heat gases and the economics involved.
Large quantity of hot flue gases is generated from Boilers, Kilns, Ovens and Furnaces. If some of
this waste heat could be recovered, a considerable amount of primary fuel could be saved. The
energy lost in waste gases cannot be fully recovered. However, much of the heat could be
recovered and loss minimized by adopting following measures as outlined in this chapter.
Heat Losses Quality
Depending upon the type of process, waste heat can be rejected at virtually any temperature from
that of chilled cooling water to high temperature waste gases from an industrial furnace or kiln.
Usually higher the temperature, higher the quality and more cost effective is the heat recovery. In
any study of waste heat recovery, it is absolutely necessary that there should be some use for the
recovered heat. Typical examples of use would be preheating of combustion air, space heating,
or pre-heating boiler feed water or process water. With high temperature heat recovery, a cascade
system of waste heat recovery may be practiced to ensure that the maximum amount of heat is
recovered at the highest potential. An example of this technique of waste heat recovery would be
where the high temperature stage was used for air pre-heating and the low temperature stage
used for process feed water heating or steam raising.

## Heat Losses Quantity

In any heat recovery situation it is essential to know the amount of heat recoverable and also how
it can be used. An example of the availability of waste heat is given below:
Heat recovery from heat treatment furnace
o

In a heat treatment furnace, the exhaust gases are leaving the furnace at 900 C at the rate
3

of 2100 m /hour. The total heat recoverable at 180 C final exhaust can be calculated as
Q = V x x C x T
p

3

## V is the flowrate of the substance in m /hr

is density of the flue gas in kg/m

p

o

## Cp (Specific heat of flue gas) = 0.24 kCal/kg/ C

Heat available (Q) = 2100 x 1.19 x 0.24 x (900-180) = 4,31,827 kCal/hr
By installing a recuperator, this heat can be recovered to pre-heat the combustion air. The fuel
o

savings would be 33% (@ 1% fuel reduction for every 22 C reduction in temperature of flue gas.
Waste heat sources ant quality:

S.No.

Source
Quality

1.

## The higher the temperature, the greater the

potential value for heat recovery

2.

## As above but when condensed, latent heat also

recoverable.

Convective and radiant heat lost Low grade if collected may be used for
from exterior of equipment
space heating or air preheats.

## Low grade useful gains if heat is exchanged

with incoming fresh water.

4.

5.

## Heat losses in providing chilled

water or in the disposal of a) High grade if it can be utilized to reduce
demand for refrigeration.
chilled water.
b) Low grade if refrigeration unit used as a
form of heat pump.

6.

the process

7.

## Heat in gaseous and liquid Poor if heavily contaminated and thus

effluents leaving process.
requiring alloy heat exchanger.

Classification
High Temperature Heat Recovery
The following Table 8.2 gives temperatures of waste gases from industrial process equipment in
the high temperature range. All of these results from direct fuel fired processes.
TYPICAL WASTE HEAT TEMPERATURE AT HIGH TEMPERATURE RANGE
FROM VARIOUS SOURCES
Types of device
Nickel refining furnace
Aluminium refining furnace
Zinc refining furnace
Copper refining furnace
Steel heating furnaces
Copper reverberatory furnace
Open hearth furnace
Cement Kiln (Dry process)
Glass melting furnace
Hydrogen plants
Solid waste incinerators
Fume incinerators

Temperature
1370-1650
650-760
760-1100
760-815
925-1050
900-1100
650-700
620-730
1000-1550
650-1000
650-1000
650-1450

## Medium Temperature Heat Recovery

The following Table 8.3 gives the temperatures of waste gases from process equipment in the
medium temperature range. Most of the waste heat in this temperature range comes from the
exhaust of directly fired process units.

## TYPICAL WASTE HEAT TEMPERATURE AT MEDIUM TEMPERATURE

RANGE FROM VARIOUS SOURCES
Types of device
Steam boiler exhaust
Gas turbine exhausts
Reciprocating engine exhausts
Reciprocating engine exhausts(turbo charged)
Heat treating furnaces
Drying and baking ovens
Catalytic crackers
Annealing furnace cooling systems

Temperature
230-480
370-540
315-600
230-370
425-650
230-600
425-650
425-650

## Low Temperature Heat Recovery

The following Table 8.4 lists some heat sources in the low temperature range. In this range it is
usually not practical to extract work from the source, though steam production may not be
completely excluded if there is a need for low-pressure steam. Low temperature waste heat may
be useful in a supplementary way for preheating purposes.

## TYPICAL WASTE HEAT TEMPERATURE AT LOW TEMPERATURE RANGE

FROM VARIOUS SOURCES
Source
Process steam condensate
Cooling water from:
Furnace doors
Bearings
Welding machines
Injection molding machine
Annealing furnaces
Forming dies
Air compressors
Pumps
Internal combustion engines

Temperature
55-88

32-55
32-88
32-88
32-88
66-230
27-88
27-50
27-88
66-120

## Air conditioning and refrigeration

condensers
Liquid still condensers
Drying,baking and curing ovens
Hot processed liquids
Hot processed solids

32-43
32-88
93-230
32-232
93-232

## Benefits of Waste Heat Recovery :

Benefits of waste heat recovery can be broadly classified in two categories:
Direct Benefits:
Recovery of waste heat has a direct effect on the efficiency of the process. This is reflected by
reduction in the utility consumption & costs, and process cost.
Indirect Benefits:
a) Reduction in pollution: A number of toxic combustible wastes such as carbon monoxide
gas, sour gas, carbon black off gases, oil sludge, Acrylonitrile and other plastic chemicals
etc, releasing to atmosphere if/when burnt in the incinerators serves dual purpose i.e.
recovers heat and reduces the environmental pollution levels.
b) Reduction in equipment sizes: Waste heat recovery reduces the fuel consumption, which
leads to reduction in the flue gas produced. This results in reduction in equipment sizes of
all flue gas handling equipments such as fans, stacks, ducts, burners, etc.
c) Reduction in auxiliary energy consumption: Reduction in equipment sizes gives
additional benefits in the form of reduction in auxiliary energy consumption like
electricity for fans, pumps etc..