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Pure Substances
Pure Substance
• In Chemistry you defined a pure
substance as an element or a
compound
• Something that can not be separated
• In Thermodynamics, we’ll define it as
something that has a fixed chemical
composition throughout
Examples
• Ice in equilibrium with water
• Air
• Air in equilibrium with liquid air is not
a pure substance – Why?
Phases of Pure Substances
• We all have a pretty good idea of what
the three phases of matter are, but a
quick review will help us understand
the phase change process
Solid
• Long range order
– Three dimensional pattern
– Large attractive forces between atoms or
molecules
– The atoms or molecules are in constant
motion – they vibrate in place
– The higher the temperature – the more
vibration
Liquid
• When a solid reaches a high enough
temperature the vibrations are strong
enough that chunks of the solid break
of and move past each other
• Short range order
– Inside the chunks the atoms or molecules
look a lot like a solid
– Ex. You only break 5% to 15% of the
water hydrogen bonds to go from solid to
liquid
Gas
• Molecules are far apart
• No long or short range order
• High kinetic energy
• In order to liquefy, lots of that kinetic
energy must be released
Solid to Liquid to Gas
• On a molecular level, the difference
between the phases is really a matter
of degree
• We identify melting points and
vaporization points based on changes
in properties
– Ex – big change in specific volume
Consider what happens when we
heat water at constant pressure
Piston
cylinder
Liquid device –
Water maintains
constant
pressure
T
5
3
2 4
1
V
Superheated
Gas
Compressed
Liquid
Two Phase
Region
Critical Point
• Above the critical point there is no
sharp difference between liquid and
gas!!
P-v Diagram of a Substance that
Expands on Freezing
P-v Diagram of a Substance that
Contracts on Freezing
Property Diagrams
• T – v diagram
• P – v diagram
• P – T diagram
P-V-T surface for pure substances
that contracts on freezing
P-V-T surface for pure substances
that expands on freezing
Property Tables
• P - pressure
• T - temperature
• v – specific volume
• u – specific internal energy
• h – specific enthalpy (h = u + Pv)
• s – specific entropy
Saturated Liquid and Saturated Vapor States
Saturation Properties
• Saturation Pressure is the pressure
at which the liquid and vapor phases
are in equilibrium at a given
temperature.
x=0 x=1
Average Properties
y y f x( yg y f )
1
y f x y fg = yg
When x = 0 we have all liquid, and y = yf
Net work done Wnet Heat supplied - Heat rejected T1 T2 dS T
Carnot 1 2
Heat supplied Qsup plied Heat supplied T1dS T1
Drawbacks of Carnot cycle
1) Steam condensation is not allowed to proceed to
completion. The condensation process is controlled one
and to be stopped at point C.
2) The working fluid at point C is both in the liquid and
vapour phase, and these do not form a homogeneous
mixture which cannot be compressed isentropically.
3) The vapour has a large specific volume and to
accommodate greater volumes, the size of the
compressor becomes quite big.
4) More power is required for running larger compressors
and hence poor plant efficiency is achieved.
5) The cycle has high specific steam consumption, large
back work ratio and low work ratio.
6) The steam at exhaust from the turbine is of low quality,
i.e. high moisture content. The liquid water droplets
causes pitting and hence erosion of the turbine blades.
Rankine cycle
Prof. Rankine modified Carnot cycle and presented a
technically feasible cycle, called Rankine cycle.
It is also a reversible cycle but differs from Carnot cycle
in the following respects.
1) The condensation process is allowed to proceed to
completion; the exhaust steam from the
engine/turbine is completely condensed. At the end
of the condensation process, the working fluid is only
fluid and not a mixture of liquid and vapour.
2) The pressure of liquid water can be easily raised to
the boiler pressure (pressure at which steam is being
generated in the boiler) by employing a small sized
pump.
3) The steam may be superheated in the boiler so as to
obtain exhaust steam of higher quality that can
prevent pitting and erosion of turbine blades.
Processes in Rankine cycle
1) Process 3–3: (Reversible adiabatic
pumping / compression - PUMP)
Rankine 1
h4 h1
h3 h2
Comparison of Carnot cycle and Rankine
cycle for the same temperature limits
Carnot Rankine
Why only Rankine cycle?
Why only Rankine cycle?
Carnot cycle needs a compressor to handle wet
steam mixture whereas in Rankine cycle, a
small pump is used.
The steam can be easily superheated at
constant pressure in a Rankine cycle.
Superheating of steam in a Carnot cycle at
constant temperature is accompanied by a fall
of pressure which is difficult to achieve in
practice because heat transfer and expansion
process should go side by side.
Therefore Rankine cycle is used as ideal cycle
for steam power plants.
Methods of improving performance of Rankine cycle
5) Regeneration process
Methods of improving performance of Rankine cycle
Increasing the boiler pressure
Methods of improving performance of Rankine cycle
Decreasing the condenser pressure
Schematic layout of
Rankine cycle with superheating
Methods of improving performance of Rankine cycle
Superheating the steam
Schematic layout of reheat Rankine cycle
Methods of improving performance of Rankine cycle
Reheating the steam between stages
Schematic layout of
regenerative Rankine cycle
Methods of improving performance of Rankine cycle
Regeneration process
Practical regenerative Rankine cycle
Features of regenerative Rankine cycle
There is improvement in cycle economy with relatively
much smaller capital expenditure.
Di-phenyl ether
Wpump h2 h1
Ideal work required
ideal
pump isentropic
Actual work required Wpump h2' h1
actual
Effect of irreversibilities on cycle efficiency
Tsat hf hg sf sg
(C) (kCal/kg) (kCal/kg) (kCal/kgK) (kCal/kgK)
540 1.80 87.3 0.0360 0.1217
205 6.92 78.7 0.0188 0.1675
Boilers
(Steam Generators)
Definition of a boiler
A boiler is a device used to generate steam at
a desired pressure and temperature by
transferring heat energy produced by burning
fuel to water to change it to steam.
It is a combination of apparatus used for
producing, furnishing or recovering heat
together with the apparatus for transferring
the heat so made available to the fluid being
heated and vaporized.
Function of a boiler
Power Generation
Transport
CLASSIFICATION OF STEAM TURBINES
Multi-shaft turbines
1 2
Energy lost due to blade friction m Vr1 Vr2
2 2
N - m/s
2
Work done on the blade(s) mVw1 Vw 2 u Vw1 Vw 2 u
Stage efficiency
Total energy supplied per stage m H 1 H 2 Hd
where H d H 1 H 2 Heat drop in the nozzle ring
MAXIMUM WORK &
MAXIMUM DIAGRAM EFFICIENCY
From the combined velocity triangle (diagram), we have
Vw1 V1 cos1 Vr1 cos 1 u and Vw2 V2 cos 2 Vr 2 cos 2 u
Vr 2 cos 2
Vw1 Vw2 Vr1 cos 1 Vr 2 cos 2 Vr1 cos 1 1 Vr1 cos 1 1 KC
Vr1 cos 1
V cos 2
where K r 2 and C
Vr1 cos 1
(or) Vw1 Vw2 V1 cos 1 u 1 KC
Rate of doing work per kg of steam per second = V1 cos 1 u 1 KC u
V1 cos 1 u 1 KC
Diagram efficiency, b 2
V1
u
Let, Blade speed ratio
V1
DISADVANTAGES
1) More friction losses due to very high velocity in the nozzles
2) Less efficiency because ratio of blade velocity to steam
velocity is not optimum
3) Power developed in the later rows is only fraction of first row.
Still all the stages require same space, material and cost.
METHODS OF REDUCING ROTOR SPEED
(PRESSURE COMPOUNDING)
METHODS OF REDUCING ROTOR SPEED
(PRESSURE COMPOUNDING)
It consists of a number of fixed nozzles which are incorporated between
the rings of moving blades. The moving blades are keyed to the shaft.
Here the pressure drop is done in a number of stages. Each stage consists
of a set of nozzles and a ring of moving blades.
Steam from the boiler passes through the first set of nozzles where it
expands partially. Nearly all its velocity is absorbed when it passes over
the first set of moving blades.
It is further passed to the second set of fixed nozzles where it is partially
expanded again and through the second set of moving blades where the
velocity of steam is almost absorbed. This process is repeated till steam
leaves at condenser pressure.
By reducing the pressure in stages, the velocity of steam entering the
moving blades is considerably reduced. Hence the speed of the rotor is
reduced. Rateau & Zoelly turbines use this method of compounding.
METHODS OF REDUCING ROTOR SPEED
(PRESSURE-VELOCITY COMPOUNDING)
1) In this method of compounding, both
pressure and velocity compounding
methods are utilized.
2) The total drop in steam pressure is carried
out in two stages and the velocity
obtained in each stage is also
compounded.
3) The ring of nozzles are fixed at the
beginning of each stage and pressure
remains constant during each stage.
4) This method of compounding is used in
Curtis and More turbines.
METHODS OF REDUCING ROTOR SPEED
(PRESSURE-VELOCITY COMPOUNDING)
REACTION TURBINE
The work done per kg of steam per second in the stage (per pair) =
muVw1 Vw2 N m / s
where, m = mass of steam flowing over blades in kg/s
Overall efficiency:
It is defined as the ratio of total useful heat drop to the total
heat supplied.
Total useful heat drop A1C1 A 2 C 2 A 3C3
Overall efficiency
Total heat supplied H A1 - h D
STEAM
CONDENSERS
Definition
Disadvantages
1) Not suitable for higher capacities
2) Condensate cannot be used as feed water to boiler
3) Air leakages are more
4) Requires larger air pump
5) Less vacuum is maintained
Surface condensers
4) Corrosion
Methods of obtaining maximum vacuum
1) Air pump
Actual vacuum
Vacuum efficiency = Maximum obtainable vacuum
Actual vacuum
Vacuum efficiency = Barometer pressure - absolute pressure of steam
Condenser Efficiency
It is defined as the ratio of difference between the outlet
and inlet temperatures of cooling water to the difference
between the temperature corresponding to the vacuum in
the condenser and inlet temperature of cooling water
Rise in temperature
Condenser efficiency= ofcooling water
Temperature
Inlet temperature
corresponding -
of cooling water
to vacuum
Air Pumps
An air pump maintains vacuum in the condenser as
nearly as possible equal to that corresponding to the
temperature of condensate by removing the air from
the condenser.
Air pumps may also remove condensate together with
air from the condenser.
A dry air pump removes the moist air alone
A wet air pump removes both air and condensate.
Types of air Pumps
Refrigeration Effect
COP
Work Input
Refrigerator vs Heat Pump
COPRefrigerator QL
COPHeat Pump QH
QH QL QH QL
Elements of a refrigeration system
1. A low temperature thermal sink to which heat
will flow from the space to be cooled.
2. Means of extracting energy from the sink,
raising the temperature level of this energy
and delivering it to a heat receiver.
3. A receiver to which heat will be transferred
from the high temperature high-pressure
refrigerant.
4. Means of reducing the pressure and
temperature of the refrigerant as it returns
from the receiver to the sink.
Methods of refrigeration
1) Ice refrigeration
2) Air refrigeration system
3) Vapour compression refrigeration system
4) Vapour absorption refrigeration system
5) Special refrigeration systems
a) Adsorption refrigeration system
b) Cascade refrigeration system
c) Mixed refrigeration system
d) Vortex tube refrigeration system
e) Thermoelectric refrigeration system
f) Steam jet refrigeration system
Reverse Carnot cycle for refrigeration
Reverse Carnot cycle for refrigeration
1) The air is expanded isentropically from points 1 to 2.
This causes the temperature to fall from T1 to T2.
2) The air is now expanded isothermally to point 3 at
temperature T2. During this process, heat is absorbed
from the cold body.
3) The air is now compressed isentropically to point 4
by the help of external power which causes the
temperature to rise to T1. During this process no heat
is absorbed or rejected by the air.
4) The air is now compressed isothermally from 4 to 1.
During this process, heat is rejected by the air to the
hot body.
Reverse Carnot cycle for refrigeration
From T-s diagram,
Heat absorbed or abstracted from cold chamber per kg of air is equal to N C p T T
1 1 4
COP
N1
C p T1 T4
T1 T4
Win C p T2 T3 C p T1 T4
T2 T3 T1 T4
Applying isentropic law for the processes 1-2 and 3-4, COP becomes,
T4
COP
T3 T4
Advantages & Disadvantages of A-R System
Advantages :
1) The refrigerant used air is non-poisonous, cheap and easily available
2) There is no danger of any kind of air leakage
3) The system is highly reliable
4) The system is highly useful for aircraft refrigeration system due to its
light weight and less space requirements in comparison to other
systems
Disadvantages :
1) Very low COP in comparison to other systems
2) Running cost is very high compared to other refrigeration systems
3) Large volume of air is required to be handled per ton of refrigeration as
compared to other systems results in larger size of compressor and
expander.
4) There is a danger of frosting at the expansion valve as air may contain
some water vapour in the case of open air system. This problem can be
partly reduced by passing air through silica gel that can highly absorb
water vapour.
Types of Air Refrigeration Systems