Laws of Thermodynamics - New
Laws of Thermodynamics - New
Laws of Thermodynamics - New
Consider 1 kg of working fluid which may be a liquid, gas or vapour, or any combination, and which is
flowing steadily through a control volume (Figure 1). The fluid may possess energy in a number of
forms between which conversions are possible:
1. Flow work or pressure work, given by pv
2. Kinetic energy C2/2 due to the movement of the fluid as a whole
3. Internal (thermal ) energy u, due to the energy of the fluid molecules
4. Potential or gravimetric energy, due to the height Z above some datum line and given by Zg
5. Chemical, electrical or magnetic energies may also be added, but these are not involved in the
overwhelming cases encountered in thermal power cycles
6. Heat Q may enter or leave the control volume
7. Mechanical energy (W) may be added or removed with some of the added energy being used to
pump the fluid into the control volume or drive it out again.
8. Accumulated (stored) energy in the control volume as a whole ecv
Control Volume
From the law of conservation of energy, the net energy input should be equal to the net energy output
plus the energy that accumulates in the control volume. For properties per unit mass (specific properties
denoted by lower case letters) and consistent energy units (J) for all terms we can write
2 2
p1v1 + C1 + u1 + gZ 1 + q1 + w1 = ecv + p2 v2 + C 2 + u 2 + gZ 2 + q2 + w2 (1)
2 2
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Energy is not usually allowed to accumulate in the control volume of practical thermal power plants
operating on thermodynamic cycles, and therefore the term ecv will be henceforth ignored and
equation 1 is reduced to
2 2
p1v1 + C1 + u1 + gZ 1 + q1 + w1 = p 2 v 2 + C 2 + u 2 + gZ 2 + q2 + w2 (2)
2 2
2 2
h1 + C1 + gZ 1 + q1 + w1 = h2 + C 2 + gZ 2 + q 2 + w2 (3)
2 2
with the terms acquiring the units of power (Nm/s, J/s or W).
For a control volume with multiple flows into and out of the system, the general steady-flow energy
equation can be written as
C12 C2
& h1 +
∑m + gZ 1 + Q& 1 + W&1 = ∑ m& h2 + 2 + gZ 2 + Q& 2 + W& 2 (5)
2 2
Boiler feed-pump: The working fluid is liquid and the difference in the potential energy terms (gZ2 -
gZ1) may be large compared with the other terms (Figure 3). The work done in raising boiler feed-water
from the level of Z1 of the exit from the condenser to the height Z2 of the point of entry to the boiler
may be an appreciable part of the load on the boiler feed-pump.
Figure 3 Control volume of a pump without heat transfer to or from the liquid
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W&1 = m& (h2 − h1 ) + m& ( gZ 2 − gZ 1 ) (6)
If (gZ2 - gZ1) is negligible, then
W&1 = m& ( h2 − h1 ) (7)
For an isentropic process, ( h2 − h1 ) = v( p 2 − p1 ) , and
W&1 = m& ( h2 − h1 ) = m& v( p 2 − p1 )
Or, since h = u + pv ,
W&1 = m& ( p 2 v2 − p1v1 ) + m& ( u 2 − u1 )
If heat is added to the system during the pumping process, the energy equation is then written as
Q& 1 + W&1 = m& ( h2 − h1 )
or
Q& 1 + W&1 = m& ( p 2 v2 − p1v1 ) + m& ( u 2 − u1 )
If the working fluid is gas the Z term or the difference (gZ2 - gZ1) is often negligible as in the case of
the gas turbine, although it is of importance when considering chimney draught.
Throttling valve: throttling valves are flow restricting devices that cause a significant drop of pressure
in the fluid without producing work. These could be in the form of a restricting valve , a porous plug or
a capillary tube (Figure 4)
The kinetic and potential energy changes and heat transfer to and from the valve (control volume) are
negligible reducing equation (4) to
h1 = h2
h = const
u + p v =u + p v (8)
1 1 1 2 2 2
u + pv = const
For a perfect gas h = cpT so that T1 = T2. In the case of an imperfect gas, the flow energy pv may
increase during the throttling process at the expense of the internal energy (u decreases) causing a drop
in temperature (Joule-Thompson cooling effect).
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Simple nozzle or diffuser: A nozzle is a device that increases the velocity of a gas or vapour at the
expense of pressure. A diffuser is a device that increases the pressure of a gas or vapour at the expense
of velocity.
The input kinetic energy, potential energy change and heat and work transfer changes are usually
negligible and the energy equation becomes
C 22
h1 = h2 + (9)
2
If the input kinetic energy is of considerable value (the gas is approaching the nozzle at a high velocity)
the energy equation for the nozzle is
C12 C2
h1 + = h2 + 2 (10)
2 2
Reciprocating internal combustion engine: The gases flow into and out of the engine slowly and the
change in kinetic energy can be neglected. Also, the potential energy change (gZ2 - gZ1) is very small
and can be ignored. The energy equation now becomes
Q& 1 = m& (h2 − h1 ) + Q& 2 + W& 2 − W&1
Figure 6 is an illustration of the representation of a control volume for a car engine. In this example, no
work is crossing the boundary into the control volume or heat crossing the boundary into or out of the
control volume.
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The energy equation is often used for the combustion and expansion (power) stroke in order to assess
the process of heat release by the burning fuel. As both the inlet and exhaust valves are closed during
this process, the process is a closed system with no added mechanical work and negligible potential
energy, flow work and kinetic energy. The energy equation in (2) is now reduced to
u1 + q1 = u 2 + q 2 + w2 , or
q1 = (u 2 − u1 ) + q 2 + w2
Both the volume and pressure change as the gases expand in the cylinder producing work w2 = ∫ pdv .
The energy equation then becomes
q1 = du + ∫ pdv + q 2 (11)
This convenient form of the energy equation equates the energy input as heat from the combustion of
the fuel to the sum of the change of internal energy of the gases as their temperature change, work done
by the gases as they expand in the cylinder during the power stroke and the heat losses to the
surroundings.
Gas turbine: The process is steady-state, steady-flow where the potential and kinetic energy changes
are negligible (Figure 7).
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Refrigeration system: A typical vapour compression refrigeration system is shown in Figure 8.
The potential and kinetic energy changes as well as the output mechanical work are assumed
negligible. The energy equation in (3) is reduced to
h1 − h2 + q1 + w1 = q 2 (13)
h1 - h2 represents the change of state of the refrigerant, q1 is the heat pumped out of the cold chamber,
w1 is the work input (usually work to run a compressor) and q2 is the heat absorbed by the cooler or
condenser. If the working fluid does not undergo a state change within the cycle,
q1 + w1 = q 2 (14)
High-speed compressor: The potential energy change, input heat, inlet velocity and output mechanical
work are negligible in the case of the compressor shown in Figure 9.
q1 = ( h2 − h1 ) = c p (T2 − T1 ) (18)
q1 = (u 2 − u1 ) = cv (T2 − T1 ) (19)
Liquid flowing at constant temperature: There is no change in internal energy, and there is no heat
or work exchange with the surroundings, and since the fluid is liquid (assumed incompressible), the
specific volume remains constant and equation (2) is reduced to
2 2
p1v + C1 + gZ 1 = p 2 v + C 2 + gZ 2
2 2
If we replace the specific volume v by 1 ρ , where ρ is the density, we obtain Bernoulli’s equation
p1 C12 p 2 C 22
+ + gZ = + + gZ (20)
ρ 2
1 ρ 2
2
• Heat transfer will occur down a temperature gradient as a natural phenomena and part of this
heat is converted to work with the balance rejected to a low temperature reservoir (Figure 10a).
• Heat can be transferred from a low-temperature reservoir up a temperature gradient to a high-
temperature reservoir with the assistance of external work (Figure 10b).
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(a) (b)
Figure 10 Schematic arrangements of a heat engine (a) and heat pump (b)
The second law of thermodynamics is also stated as the Law of Degradation of Energy whereby the
quantity of energy is conserved, but its quality (the potential to produce useful work) is not. Every time
energy changes from or is transferred from one system to another, its potential to produce useful work
is reduced irreversibility for ever. It is then said that energy has degraded.
This law is the reason we may face an energy crisis. All the energy that we use ultimately ends up as
waste heat transferred to the earth’s atmosphere and then to space.
• If heat is added to a system dQ will be positive and ds will be positive (entropy increases).
• If heat is removed from a system dQ will be negative and ds will also be negative (entropy
decreases)
• If ds = 0 during a process the process is isentropic. The frictionless adiabatic process is an
isentropic process.
A reversible process occurs when both the system and the surroundings are returned to their original
conditions after the process and reverse process have been carried out. Processes in nature are however
irreversible because reversal always causes some change to occur in the system and/or surroundings.
Factors causing irreversibility include:
• Friction
• Unrestricted expansion
• Heat transfer through a finite temperature difference
• Mixing of two different gases
• Chemical reactions.
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THE ZEROTH LAW OF THERMODYNAMICS
If two systems are in thermal equilibrium with a third system, then they are in thermal equilibrium with
each other and the three systems are said to be at the same temperature.
This law was added to the laws of thermodynamics early in the 20th century because it was realized that
the concept of equal-in-temperature is a prerequisite to a logical development of those laws. And to be
logical, it was named the Zeroth Law of thermodynamics.
We should know first just what it is that temperature measures. If we look in the dictionary, we read
that temperature measures the relative "hotness" of things. But this definition in reality tells us nothing,
for when we look up hotness, the dictionary blandly tells us that it is something characterized by high
temperature. Here the kinetic theory helps us out of our dilemma. According to this theory, the pressure
of a gas varies directly with the kinetic energy of its molecules. But according to the gas laws, we can
see that the pressure of a gas also varies directly with the absolute temperature. Therefore, we may
conclude that the kinetic energy of molecules also varies directly as the absolute temperature, and is in
fact what temperature actually measures. The higher the molecular agitation the higher the temperature,
and the slower the molecular movement the lower the temperature becomes, until there would be no
temperature or pressure at all if we could somehow cool the gas to where the molecules were frozen
motionless.
Thomson (Lord Kelvin) was very much aware of this perplexing problem. The answer came to him in
1848 during his pondering on the significance and implications of Carnot's reversible cycle. He had the
acuity to see that here was a means of establishing a universal and absolute temperature scale,
independent of any thermometric substance and based only on energy conversion.
To show how it is possible to arrive at an absolute scale, we shall first perform a hypothetical
experiment showing that an absolute zero of temperature must exist, and then extend this line of
reasoning to develop an "energy" or "thermodynamic" temperature scale.
Let us set up a small Carnot reversible engine to operate between a high-temperature region and a low-
temperature region as shown in Figure 11.
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Figure 11 The Carnot reversible engine
Since no engine can have a higher efficiency than the Carnot engine, the ratio of heat received to heat
rejected has a unique value when operating between temperatures (1) and (2).
Q1 T1 Q2 T2
= or =
Q2 T2 Q1 T1
where T represents a property called temperature on some thermodynamic scale which is independent
of any thermometric substance.
We have defined thermal efficiency of a heat engine as the work done divided by the heat received
W
thermal efficiency =
Q1
But according to the First Law of Thermodynamics heat energy cannot be destroyed, and therefore the
difference between the heat received and heat rejected by the cycle must be the work done, i.e.
Ql - Q2 = W. Making this substitution, then, we have,
Q1 − Q2 Q
thermal efficiency = or 1 − 2
Q1 Q1
Now substituting the temperature ratio for the heat ratio as shown in the first equation, we have,
T
thermal efficiency = 1 − 2 (21)
T1
From this expression of thermal efficiency we must conclude that T2, the temperature of the receiver,
can never be zero or less than zero. For if T2 were equal to zero, we see that the thermal efficiency of
the heat engine would be 1, or 100 per cent. This is inconceivable, since it would result in a complete
conversion of heat to work in a heat engine and would constitute a violation of the Second Law of
Thermodynamics. Also, if T2 were less than zero (a negative number), the thermal efficiency would be
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greater than 100 per cent which would mean a reversal of the direction of Q2, and thus heat would be
drawn directly from the low-temperature reservoir. This likewise would be a violation of the Second
Law. So, in theory, we can approach infinitely close to an absolute zero of temperature but never quite
attain it.
Next let us continue our hypothetical experiment by operating our little Carnot engine between a high-
temperature reservoir at the temperature of boiling water, T1, and a low-temperature reservoir at the
temperature of melting ice, T2. Suppose we had some metering device that could measure the amount
of heat received, Qsteam and the amount of heat rejected, Qice. If we actually were able to make these
Qsteam
measurements, we would find that = 1.3662 . But from our previous reasoning we note that
Qice
this must also be the ratio of the thermodynamic temperature of these two points. Thus,
Qsteam Tsteam
= = 1.3662 (22a)
Qice Tice
We might decide that we wanted, let us say, 100 divisions or degrees to separate the temperature of
boiling water and the temperature of melting ice on a scale called “Centigrade scale or C for short”.
Then we have
Tsteam – Tice =100oC (22b)
Here we have two equations with two unknowns, and by solving them simultaneously we can calculate
the temperature of boiling water and melting ice on a thermodynamic scale:
Tsteam = 373.07
degrees Kevin, K
Tice = 273.07
If we decide to have another scale where 180 divisions or degrees separate the temperature of boiling
water and the temperature of melting ice (Fahrenheit scale, F), then
Tsteam – Tice =180o which leads to
Tsteam = 672
degrees Rankine, R
Tice = 492
The Third Law allows the determination of absolute entropies from thermal data. Knowing the absolute
o
entropy at a reference state ( s ), the absolute entropy of a substance at any other state is given by
T ,p
o
sT , p = s + ∫ ds (23)
To , p o
The reference state is usually taken at 0.1 MPa and 25oC.
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dT dp
ds = Cp −R (24)
T p
T p
o dT dp
sT , p = s + ∫ Cp −R ∫
To T po p
o T dT p
sT , p = s + ∫ C p − R ln (25)
To T po
so
The absolute entropies at 298 K and 0.1 MPa are known for most substances and the entropy change
ds for an ideal gas at any temperature other than the reference temperature can be determined if C p is
known at that temperature. Thermodynamic tables such as the JANAF tables list the absolute entropy
o
values for substances at a constant pressure of 0.1 MPa as a function of temperature; i.e. the value s
o T dT
so = s + ∫ C p (26)
To T
Equation (25) is used to calculate the absolute entropy values at pressures other than the reference
pressure of 0.1 MPa. When using equation (25) for chemical reactions, the pressure ratio in the last
term is replaced by the mole concentration of each substance.
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Figure 12 h-s diagram of the expansion process in an adiabatic turbine
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Figure 13 h-s diagram of the compression process in an adiabatic compressor
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T1 − T2 s
ηn = (32)
T1 − T2 a
∗
A process occurs when a system changes from one state to another. Thus, when air in a cylinder at an initial state with
properties V1 and T1 is heated, the volume may increase and the temperature may rise at a final state having properties V2
and T2
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Figure 15 Ideal Carnot Engine and Cycle
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APPENDIX B
Consider an axial compressor comprising several infinitely small stages. The small stage efficiency ηp
is defined as the constant isentropic efficiency for each small stage (Figure1).
In differential form
dTs γ − 1 dp dT γ − 1 dp
= , or η pc =
T γ p T γ p
Integrating between points 1 and 2, keeping in mind that ηpc is by definition constant, we obtain
ln( p2 p1 )( γ −1 ) γ
η pc = (2)
ln( T2 a T1 )
This equation enables to calculate ηpc from the known values of p and T at the inlet and outlet of
compressor. Rearranging equation (2) yields
T2 a p ( γ −1 ) γη pc
=( 2 ) (3)
T1 p1
ln(T1 T2a )
η pt = γ −1
ln( p1 p2 ) γ
T2 s p
− 1 ( 2 )( γ −1 ) γ − 1
∆T T − T T p1
ηc = s = 2 s 1 = 1 = (4)
∆T T2 a − T1 T2 a − 1 ( p2 )( γ −1 ) γη pc − 1
T1 p1
This equation enables to determine the variation of ηc with the compressor pressure ratio for a given
polytropic efficiency ηpc. As Figure 2 shows, the compressor isentropic efficiency decreases with
increasing pressure ratio at constant polytropic efficiency (0.9). For an irreversible adiabatic
(polytropic) process
dT n − 1 dp dT γ − 1
= and =
T n p T γη pc
γ −1 n−1
=
γη pc n
dT γ − 1 dp
and since = ,
T γη pc p
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γ −1 n −1
∴ = (5)
γη pc n
hence the origin of the term polytropic efficiency.
A similar expression can be obtained for the expansion process in a multistage turbine by defining the
efficiency of an infinitely small expansion stage (Figure 3)
By definition
dTa
η pt = = const
dTs
(6)
T1 p η ( γ −1 ) γ
= ( 1 ) pt
T2 a p2
T2 a p η ( γ −1 ) / γ
1− 1 − ( 2 ) pt
T −T T1 p1
ηt = 1 2 a = = (7)
T1 − T2 s T p
1 − 2s 1 − ( 2 )( γ −1 ) γ
T1 p1
The variation of the isentropic efficiency of the turbine as function of pressure ratio at constant
polytropic efficiency of 0.9 is shown in Figure 2 . The temperature equivalents (in terms of stagnation
temperatures) of the work transfers for a given pressure ratio for both the compressor and turbine
respectively are
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(γ − 1) γ η
pc
p
= T − 1
2
T −T (8)
2t 1t 1t
1
p
(γ − 1 )η
pt
γ
p
= T 1 −
2
T −T (9)
1t 2t 1t
p
1
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