Chapter 2 – Thermodynamics Review

• Introduction
• The First Law and the Open System
• The First Law and the Closed System
• The Cycle
• Property Relationships
• The Second Law of Thermodynamics
• The Concept of Reversibility
• The Concept of Entropy
• The Carnot Cycle
2.0 Heat, work, and the system
• Heat is a form of energy which is transferred from one body to another
body at a lower temperature, by virtue of the temperature difference
between the bodies
• If body A is at 15°C, while body B is at 20°C, heat will be
transferred from A to B, until both bodies come at same temperature.
• Once both bodies are at same temperature, it is called Thermal
Equilibrium,
• Thermal insulation around A and B is provided, that heat transfer
does not take place between bodies and surroundings. In that case,
thermal equilibrium will be achieved when the temperatures of A, B
and surroundings is equal.
• A system may be defined as a collection of matter within
prescribed and identifiable boundaries.
• The boundaries can be flexible, or inflexible.
• For example, in a reciprocating engine the boundaries are
cylinder walls and the piston. The volume changes between
compression and suction stroke, i.e. during the cycle.
• As a result, the piston moves so do the boundaries move. The
system to be considered, remains within the boundaries.
• This type of system is known as a closed system since there is no
transfer of mass across the boundaries. All the studies of
conversion of mass or energy is done within the boundaries
• An open system is one where energy and mass cross the
boundaries of that system.
• An open system in the transient state is the one in which the mass
inflow and outflow are not equal or vary with time and in which
the mass within the system changes with time.
• For example, the fluid in a turbine at any instant may be defined
as an open system whose boundaries are shown in Figure.
The state of the working fluid
• In practice the matter contained within the boundaries of the system
(which are being analysed) can be liquid, vapor, or gas. Such as steam in
steam turbines, air fuel mixture after combustion, for gas turbines, etc.
• We call it working fluid.
• At any instant the state of the working fluid may be defined by certain
characteristics called its properties.
• The thermodynamic properties used, are pressure, temperature, specific
volume, specific internal energy, specific enthalpy, and specific entropy.
• For any pure working fluid, only two independent properties are sufficient
to define the state of a system.
• If, a state 1 is defined against p and v,. The
temperature can be determined.
• Using this data, p T or Tv for condition 1 and 2
can be determined
Reversibility
• Once the state of a fluid can be represented by a point located on a
diagram using two properties as coordinates.
• When a system changes state in such a way that at any instant during (a)
the process the state point can be located on the diagram, then the
process is said to be reversible.
• The fluid undergoing the process passes through a continuous series of
equilibrium states. A reversible process between two states can
therefore be drawn as a line on any diagram of properties Figure (a)
• In practice, the fluid undergoing a process cannot be kept in
equilibrium in its intermediate states and a continuous path cannot be
traced on a diagram of properties.
• Such real processes are called irreversible processes.
• An irreversible process is usually represented by a dotted line joining the end
states to indicate that the intermediate states are indeterminate Figure (b)

When a fluid undergoes a reversible process, both the fluid and its
surroundings can always be restored to their original state.
Reversible work
• Consider an ideal frictionless fluid contained in a cylinder behind a piston.
• Assume that the pressure and temperature of the fluid are uniform and that there is no
friction between the piston and the cylinder walls.
• Let the cross-sectional area of the piston be A, let the pressure of the fluid be p
• The force exerted by the piston on the fluid = pA.
• Let the piston move under the action of the force exerted a distance dl to the left.
• Then work done on the fluid by the piston is given by force times the distance moved, i.e. Work
done, dW = - (pA) x dl= - p dV
• where dV is a small increase in volume.
• The negative sign is necessary because the volume is
decreasing.
• For a mass m, work is dW = - m p dv where v is the
specific volume.
• When a fluid undergoes a reversible process a series of state
points can be joined up to form a line on a diagram of
properties.
• The work done on the fluid during any reversible process, W,
is therefore given by the area under the line of the process
plotted on a p-v diagram
•
Example 1.3:
In a certain steam plant the turbine develops 1000 kW. The heat
supplied to the steam in the boiler is 2800kJ/kg, the heat rejected by
the steam to the cooling water in the condenser is 2100 kJ/kg and
the feed-pump work required to pump the condensate back into the
boiler is 5 kW. Calculate the steam flow rate.
Solution
• The cycle is shown diagrammatically in Fig.
• A boundary is shown which encompasses the entire plant.
• Strictly, this boundary should be thought of
as encompassing the working fluid only.
• For unit mass flow rate:
The non-flow equation
• In the last section it is stated that when a system possessing a certain intrinsic energy (sum of
internal, kinetic and potential energy) is made to undergo a cycle by heat and work transfer, then
the net heat supplied plus the net work input is zero.
• This is true for a complete cycle when the final intrinsic energy of the system is equal to its initial
value.
• Consider now a process in which the intrinsic energy of the system is finally greater than the initial
intrinsic energy.
• The. sum of the net heat supplied and the net work input has increased the intrinsic energy of the
system, i.e. Gain in intrinsic energy = Net heat supplied + net work input
• When the net effect is to transfer energy from the system, then there will be a loss in the intrinsic
energy of the system.
• When a fluid is not in motion then its intrinsic energy per unit mass is known as the specific
internal energy of the fluid and is given the symbol u.
• The internal energy of mass, m, of a fluid is written as U, i.e. mu = U.
•
Example 1.4
In the compression stroke of an internal-combustion engine the heat rejected to the cooling water is
45 kJ/kg and the work input is 90 kJ/kg. Calculate the change in specific internal energy of the
working fluid stating whether it is a gain or a loss.
Example 1.5
In the cylinder of an air motor the compressed air has a specific internal energy of 420 kJ/kg at the
beginning of the expansion and a specific internal energy of 200 kJ/kg after expansion. Calculate the
heat flow to or from the cylinder when the work done by the air during the expansion is 100 kJ/kg.
Steady State Open System
• Steady-state open system, is also called as the
steady-state steady-flow (SSSF) system.
• In this system, mass and energy flows across the
boundaries do not vary with time and in which the mass
within the system remains constant.
• The SSSF system, applicable to mechanical energy is
shown schematically in Figure
• The first law equation will be applied as:

PE1 + KE1 + IE + FE1 +∆Q = PE2 + KE2 + IE + FE2 +∆Wsf

• where the subscripts 1 and 2 indicate the inlet and

exit stations of the open system.
Explanation of Terms:

Where:
• m is the mass of a quantity of matter or fluid entering and leaving the system (both equal in
SSSF),
• z is the elevation of stations 1 or 2 above a common datum,
• g is the gravitational acceleration, and
• gc is a conversion factor numerically equal to 32.2 lbm • ft/(lbf • s2) or 1.0 kg • m/(N • s2)
•
•
For constant specific heat or for small change in temperature the above equations can be rewritten
as
• It may be noted that U + PV is enthalpy H whether the system is open or closed (below).
• In the open system PV is the flow energy. Whereas,
• In the closed system PV is simply the product of pressure times volume.
• The above equations are generally used to solve the problems, however, depending on
process some values change significantly, while others remain unchanged or go through
insignificant change.
• Some Examples will be discussed now:
The Cycle
• In order to convert forms of energy, particularly heat, to work on an
extended or continuous basis (our main objective), one needs to
operate on a cycle.
• A process begins at one state of the working fluid and ends at another,
and that is that.
• A cycle, on the other hand, is a series of processes that begins and
ends at the same state and thus can repeat indefinitely, or as long as
needed.
• An example is the ideal diesel cycle, shown on the P-V and T- s
diagrams in Figure. It is composed of:
• Adiabatic (no heat exchanged) compression process 1-2,
• a constant-pressure heat addition process 2-3,
• an adiabatic expansion process 3-4,
• a constant volume heat rejection process 4-1, which returns the
cycle back to 1.
• Because the beginning and the end of the cycle is 1 (or any other
point), a thermodynamic cycle is a closed system
•
Property Gas Relationship – Perfect Gas
• Equation of State for perfect gas
Vapors
• The enthalpy of steam mixed with water is given by:
h = hf + x hfg

• x is dryness fraction i.e. mass of dry vapor in 1kg of mixture. For dry saturated mixture x =1
and for dry saturated steam it is 0
• hf is enthalpy of fluid, i.e. saturated liquid
• hfg is the difference between enthalpy of fluid and enthalpy of saturated vapor i.e.
hfg = hg - hf

• Similar equations are written for specific volume and entropy as:
v = vf + x vfg
s = sf + x sfg
Second Law of Thermodynamics
• First law of thermodynamics deals with conservation of energy, declaring that all forms of
energy are convertible to one another,
• The second law puts a limitation on the conversion of some forms of energy to others.
• We are most concerned with two forms, heat and work.
• The second law does not negate the equivalence of conversion of these two, only the
extent
• In practice, work can be continuously converted to heat. But --- Heat cannot be
completely and continuously converted to work.
• In other words, heat is not entirely available to do work on a continuous basis, i.e., in a
cycle (though it may be in a process).
• The portion of heat that cannot thus be converted to work, called unavailable energy, has
to be rejected as low-grade heat after the work has been done.
• The portion of heat that cannot thus be converted to work, called unavailable energy, has
to be rejected as low-grade heat after the work has been done
• Following are few historical statements that convey the idea of second law of thermodynamics
• The Kelvin-Planck statement. “It is impossible to construct a device which will operate in a cycle
and produce no effect other than the raising of a weight and the exchange of heat with a single
reservoir”
• In this statement:
• “operate in a cycle” means operate continuously,
• “raising of a weight” means doing work, and
• “exchange of heat with a single reservoir” means heat is only added, not rejected, and that
there is a thermal efficiency of 100 percent.
• Figure shows a device that violates the Kelvin-Planck statement.

Heat Source
A device that violates the Kelvin-Planck statement of the
QA second law – Heat is just being converted to work???

Heat Engine W
• The Clausius statement. “It is impossible, to construct a device
which operates in a cycle and produces no effect other than the
transfer of heat from a cooler to a hotter body”.
• Figure shows a device that operates between a high-temperature
reservoir and a low-temperature reservoir.
• A reservoir is a source of heat or a heat sink large enough that it
does not undergo a change in temperature when heat is added or
subtracted from it. (sea or river)
• The device in Figure produces no effect other than the transfer
of heat from the low-temperature reservoir to the
high-temperature reservoir, hence, it produces (or absorbs) zero
work.
• By the first law, with this device as a system, the heat QL
received from the low-temperature reservoir is equal to that
delivered to the high-temperature reservoir
A device that violates the Clausius
statement of the second law
• Simply speaking,
• The Second Law of Thermodynamics, indicates that in any complete cycle the gross heat
supplied plus the net work input must be greater than zero.
• Thus for any cycle in which there is a net work output (i.e. W = -ve), heat must always be
rejected.
• For any cycle in which heat is supplied at a low temperature and rejected at a higher
temperature there must always be a positive work input.
• This law will be further discussed in Heat Engines
Concept of Reversibility
• As we have discussed, a reversible process, also called an ideal
process, is one which can reverse itself exactly by following the same
path it undertook in the first place and thus restore to the system or the
surroundings the same heat and work previously exchanged.
• An ideal cycle can be called reversible, when it can trace its exact path
back from 2. to 1 and thus give back the exact work of compression
done upon it from 1 to 2.
BUT
• there are no ideal, and no reversible, processes in the real world.
• Real processes are irreversible, although the degree of irreversibility
may vary from process to processes. – Our efforts focus on making it
closer to ideal cycle (Process) and thus improve efficiency…..
• There are many sources of irreversibility in nature. Four of those are
most important.
• These are (a) friction, (b) heat transfer, (c) throttling, and (d) mixing.
• Friction: Mechanical friction is one in which mechanical work is dissipated into a heating effect,
such as in the case of a shaft rotating in a bearing.
• Additional energy is required to overcome friction.
• Thus friction is the dissipation of energy that otherwise could have been transformed to useful
work.
• Fluid friction is similar to mechanical. A fluid expanding behind a piston or through a turbine
undergoes internal friction, resulting in the dissipation of part of its energy into heating itself
at the expense of useful work.
• The fluid then does less work and exhausts at a higher temperature (or enthalpy) than it would
had this fluid friction not existed.
• The more irreversible the process, the more the heating effect and the less the work.
• Heat transfer: Heat transfer in any of its forms, conduction, convection, or radiation,
occurs from a higher temperature to a lower temperature.
• Heat transfer causes a loss of availability because no work is done between the high-
and low-temperature bodies.
• It cannot reverse itself without the help of an external aid (a heat pump) – Loss of Power/ work
• It also follows that the larger the temperature difference between the two bodies, the larger the
loss of availability (i.e., the loss of potential work),
• and the larger the irreversibility.
• All power systems employ heat-transfer processes from a primary source, such as combustion
gases or nuclear-reactor primary coolant, to a working fluid. Increased losses will directly
impact, power generation
• It is thus important to reduce the temperature differences across the heat exchanger to the
minimum practicable, to reduce this source of irreversibility, which is a primary cause of
reduction in efficiency of real systems. (Insulation, Maximum Heat Transfer between fluids,
temperature difference in turbine, etc.)
• Throttling: Throttling is an uncontrolled expansion process of a fluid from a high
pressure (and occasionally high-temperature) region to a low-pressure region. Examples
are leakage from a steam pipe or the flow through a valve.
• No work is done and heat transfer across the narrow opening is negligible.
• The resulting high kinetic energy is dissipated in fluid friction and restore the enthalpy of the
fluid to its original value.
• Throttling is irreversible because flow cannot be from the low-pressure region to the high
pressure region.
• It results in the loss of availability, i.e., the loss of work that could have been otherwise
obtained if expansion between the two regions occurred ideally behind a piston or through a
turbine.
• It follows that the greater the pressure difference in throttling, the greater the irreversibility.
• Throttling should be avoided or minimized in power systems
• Mixing: When two or more separate fluids or gases are made to mix or diffuse into each other,
they cannot unmix without external aid.
• Hence mixing is an irreversible process that results in the loss of availability of the constituent
fluids.
• Mixing is unavoidable in many cases, such as when fuels and air are prepared for combustion
or
• when steam and colder water mix in certain devices, such as open feed water heaters.
• It is not, however, as major a concern in power systems as fluid friction or heat transfer.
Concept of Entropy
• Entropy is a property, as are pressure, temperature, internal energy, and
enthalpy
• Its units are Btu per degree Rankine (Btu/°R) or the units Joule per
degree kelvin (J/K).
• Its symbol is s.
• Specific Entropy s is frequently used in Thermal Power Generation,
the units are J/(kg.K) or Btu/(lbm.°R)
• We know that for a non-flow work, (ideal or reversible) the expression
is:

• Graphical representation of non flow work is (area under the curve)

•
•
• This leads to one physical attribute of entropy that it remains constant in an
adiabatic reversible process.
• This is much like temperature being the property that stays constant in an
isothermal process or pressure in a constant pressure process, etc.
• Let us now assume that the expanding fluid is a perfect gas (though we can
easily come to the same conclusions using a vapor or a mixture of liquid and
vapor.)
• Lines P1 and P2 are constant-pressure lines for a perfect gas on the T-s plane
where P1 > P2.
• Their shape can be ascertained from the perfect-gas relationship:

• Let us further assume that the gas starts at 1 and expands adiabatically to
pressure P2.
• We know that if the process is reversible as well as adiabatic, entropy remains
constant and the process is represented by 1-2s.
• Our problem in TPG is process is adiabatic but irreversible.
• We know that irreversibility results in increase in temperature of the gas leaving
at pressure P2, point 2, beyond that for the adiabatic reversible process i.e. 2.
• Thus T2 > T2s on the P2 line, which curves upwards,
• This can only occur if the entropy at 2 is greater than at 2s,.
• A more irreversible expansion results in greater self-heating of the gas and the
process would be 1-2', etc.
• The conclusion is: The greater the irreversibility, the greater the increase in
entropy in an adiabatic process. (Example: Turbine Vacuum)
• If the expansion were to occur in a turbine, the work is obtained from the first law
(which applies equally to reversible and irreversible processes) for the three
processes as:
• =H1-H2s
• =H1-H2
• =H1-H2’
• It is obvious that T1>T2s>T2’, Consequently, the ∆T is decreasing. Resulting the
work is also reducing at temperature is increasing, since dh = cp dT
• The Limiting Case
• The process 1-2t, is one of constant temperature (See horizontal line) and
hence, for a gas, constant enthalpy
• This is just a throttling process where the work ∆H is zero and all energy is
dissipated in fluid friction.
• This is the most irreversible process and the one with the most increase in
entropy
• The degree of irreversibility is given by an expansion or turbine efficiency called
the polytropic turbine efficiency ηT
• It is also called the isentropic or adiabatic turbine efficiency, which is equal to the
ratio of actual work to ideal work and is given by:

• For constant specific heats:

•
For constant specific heats:
• We can now state that
• the change of entropy is a measure of the unavailable
energy, (If the entropy remains constant, unavailable
energy is zero)
• This leads us to an important physical meaning of entropy,
that entropy is a measure of irreversibility, or more
generally: Entropy is a measure of disorder. More
irreversibility, less work, or less output
• In the case of vapors, when expansion between P1 and P2 ends in the
two-phase region, shown on both T-s and h-s (Mollier) charts,
• In this case the same observation (as for the gases applies) except
that the exit temperature is the same for the adiabatic reversible and
adiabatic irreversible processes because they are both in the
two-phase region.
• The exit enthalpy is, however, greater than in case of the irreversible
process h2 > h2s and the work is less: because h1 - h2 < h1 - h2s,.
• The degree of irreversibility here is given by a turbine efficiency, the
same as in Equation above, i.e.

• For constant specific heat:

• In the case of pumping liquids, a pump efficiency ηp , given by the

ratio of ideal work to actual work, is used to obtain the actual work.
• Using Eq. (l-22a), actual work:
The Carnot Cycle
• Sadi Carnot laid the foundations of the second law of thermodynamics,
• He introduced the concepts of reversibility and cycles, and introduced
the principle that the temperatures of the heat source and heat sink
determined the thermal efficiency of a reversible cycle.
• He also postulated that because all such cycles must reject heat to the
heat sink, efficiency is never 100 percent
• To show this, and to show that the effect of the working fluid on the
thermal efficiency of a reversible cycle is nonexistent, Carnot invented
his famous, though hypothetical (one cannot build a reversible engine),
• The Carnot cycle, shown on the P-V and T-S diagrams, is composed of
four processes:
1. 1-2: reversible adiabatic compression
2. 2-3: reversible constant-temperature heat addition
3. 3-4: reversible adiabatic expansion
4. 4-1: reversible adiabatic heat rejection
• The thermal efficiency of the Carnot cycle ηC can now be easily obtained, noting that the change
in entropy during heat addition and rejection are equal in magnitude.
• Thus:

• TH and TL are temperatures of Heat Source and Sink

• Noting that the Carnot cycle is completely reversible (hypothetical),
• Thus heat transfer between the heat source and the working fluid occurs, hypothetically, across a
zero temperature difference.
• Hence TH = T2- Similarly TL = T1
For all power cycles the net work and the thermal efficiency are defined by
•