Chemical Thermodynamics-I

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Phase behavior of a pure component

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Phase behavior of a pure component

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 Boiling points and vapor pressures of water [1]

Please go through steam table and see the other values of

saturated pressures (vapor pressures) against saturated
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temperatures (boiling points).
Phase behavior of a pure component [1]

H 2O

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Phase behavior of a pure component [1]

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Phase behavior of a pure component [1]

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Experimental p-v diagram of CO2 [2]

Critical isotherm = 304.19 K

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T-h diagram of a pure component

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p-T diagram of a pure component [1]

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p-T diagram of a pure component

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 pvT surface of a pure component [1]
Contracts on freezing

Expands on freezing
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Pvt surface of an ideal gas [3]

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Pressure-enthalpy diagram of NH3

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Pressure-enthalpy diagram of CH4

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 Working fluids

o For our study of thermodynamics, we will classify the

working fluids into two categories:
Ideal gas and real fluid such as steam or liquid water.

oProperties of liquid and gaseous water are plotted in

three tables. One for subcooled region, second for
saturated region, and third for superheated region.

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 Steam tables

Properties of liquid and gaseous water are plotted

in three tables. One for subcooled region, second
for saturated region, and third for superheated
region.

You may need single- or double-interpolation

while using such tables.

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A part of saturated steam table: temp. table [1]

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A part of saturated steam table: press. table [1]

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A part of superheated table [1]

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T-s diagram of water [1]

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Mollier (h-s) diagram of water [1]

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 Power cycle
A power cycle is used to produce useful (net work
output) by a given amount of heat supplied.

Power cycles may be a

1) gas power cycle or

2) vapor power cycle.

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 Power cycle
Vapor power cycle: A power cycle in which the
working fluid undergoes condensation (becomes
liquid) and vaporization (becomes vapor) in
various processes that constitute a complete cycle.

Gas power cycle: For a gas power cycle, the

working fluid is in a gaseous state at all points of
the cycle.

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Carnot vapor power cycle

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Carnot vapor cycle

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 Carnot vapor power cycle
What will be the pv diagram of Carnot vapor
power cycle?

The impracticalities associated with Carnot vapor

power cycle makes it unsuitable for practical
applications. Vapor power plant is therefore built
on Rankine cycle.

What are the practical issues with Carnot vapor

cycle?
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Rankine cycle [1]

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Ideal Rankine cycle [1]

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 Energy balance for each unit
Write down the total energy balance (First Law of
Thermodynamics) for each unit and neglect the
terms having negligible contribution towards
energy balance equation. Here, each of the devices
is as an open system and not a closed system.

See class notes.

To analyze a given cycle, it is simple, just find the

conditions of steam at each point (1 to 4) and find the
enthalpy at each point and using enthalpy values, calculate
heat supplied, heat rejected, and so on… 30
Non-ideal Rankine cycle [1]

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 Increasing thermal efficiency
How to increase the efficiency of the cycle?

• Lowering the condenser pressure

• Increasing degree of superheat
• Increasing boiler pressure

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Lowering the condenser pressure [1]

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Increasing degree of superheat [1]

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Increasing boiler pressure [1]

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 Increasing boiler pressure
What is the disadvantage of using increased
pressure in the boiler?

The turbine exit is at a lower dryness fraction

which hurts turbine. One way of improving the
quality (dryness fraction) of vapor at the turbine
outlet is to reheat the vapor leaving the turbine and
to use two turbines: A high pressure turbine and a
low pressure turbine.

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Reheat cycle [1]

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Example 10-1 [1]

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 Activity
Draw the cycle discussed on the last slide on T-s
diagram and h-s diagram of water and workout
heat supplied, heat rejected, work output, work
input, and thermal efficiency of the cycle.

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Problems [1]

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Problems [1]

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Problems [4]

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Gas power cycles [1]

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Carnot gas power cycle [1]

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 Gas power cycle
What will be the pv diagram of Carnot gas power
cycle?

What are the impracticalities associated with

Carnot gas power cycle that makes it unsuitable
for practical applications?

Isothermal heat transfer requires very large heat

exchangers and long time of contact which is not
practical to build and operate. This is why Carnot
gas power cycle is not a practical cycle.
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Carnot gas power cycle [1]

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 Brayton cycle
Brayton cycle (gas turbine cycle) is the basis of
practical gas power cycles. Brayton cycle is either
open or closed gas turbine cycle. If all the
processes involved are ideal, the process is called
as ideal Brayton cycle.

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Open gas turbine cycle [1]

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Closed gas turbine cycle [1]

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Closed gas turbine cycle [1]

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Closed gas turbine cycle [1]

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Closed gas turbine cycle [1]

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Carnot gas power cycle [1]

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Air standard assumption [1]

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Mathematical analysis of the closed gas turbine
cycle
Again applying energy balance on each unit, one
can find the performance equation of each unit and
the thermal efficiency of the cycle. Use the
definition of specific heat capacity and ideal gas
relationships to workout the various applicable
relationships.

See class notes.

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Example [4]

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Otto cycle [1]

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Otto cycle [1]

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Otto cycle [1]

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 Mathematical analysis of Otto cycle

Again applying energy balance on each unit, one

can find the performance equation of each unit and
the thermal efficiency of the cycle. Use the
definition of specific heat capacity and ideal gas
relationships to workout the various applicable
relationships.

See class notes.

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Otto cycle[1]

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Otto cycle[1]

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 Example [4]

An Otto cycle is to have a compression ratio of 8.

Air at the start of compression is at 300 K and the
heat to supplied is to be 2500 kJ/kg. What are the
temperatures at the end of compression, at the start
of expansion, and at the end of expansion? What
are the net work per kg and the thermal efficiency
for the cycle?

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Diesel cycle[1]

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 Diesel cycle
What are the four processes of Diesel cycle? How
are these different from Otto cycle? Draw T-s
diagram of ideal Diesel cycle.

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 Mathematical analysis of Diesel cycle

Again applying energy balance on each unit, one

can find the performance equation of each unit and
the thermal efficiency of the cycle. Use the
definition of specific heat capacity and ideal gas
relationships to workout the various applicable
relationships.

See class notes.

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Diesel cycle[1]

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 Cycle efficiencies
Otto cycle:

r is compression ratio = v1/v2

Diesel cycle:

rc is cut off ratio = v3/v2

Closed Brayton cycle:

rp is pressure ratio = p2/p1

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Problems [4]

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Problems [1]

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Problems [4]

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 Refrigeration
In refrigeration, heat flows from a lower
temperature to a higher temperature, i.e., to keep
the refrigerated space at a lower temperature than
the temperature of the surroundings. The working
fluid in a refrigeration system is called as
refrigerant.

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Carnot refrigeration cycle [1]

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 Vapor-compression refrigeration cycle
Why Carnot refrigeration cycle is not practical to
build? What about compression of and expansion
of a wet vapor?

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 Vapor-compression refrigeration cycle
Vapor-compression refrigeration cycle is a widely
used refrigeration cycle. In vapor-compression
refrigeration cycle, the refrigerant is vaporized and
condensed alternately and the refrigerant is
compressed in the vapor phase. The expansion
engine or turbine in the Carnot cycle is replaced
with an expansion valve (throttling process).
Expansion through a constriction is an irreversible
process. Note there is no work output in the
throttling process and the expansion process is
isenthalpic (constant enthalpy process).
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Vapor-compression refrigeration cycle [1]

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Vapor-compression refrigeration cycle [1]

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Vapor-compression household refrigerator [1]

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Vapor-compression refrigeration Chiller [4]

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Vapor-compression refrigeration cycle [1]

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Vapor-compression refrigeration cycle [1]

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 Energy balance for each unit
Write down the total energy balance (First Law of
Thermodynamics) for each unit and neglect the
terms having negligible contribution towards
energy balance equation. Here, each of the devices
is as an open system and not a closed system.

See class notes.

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Example 11.1 [1]

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 Activity
Draw the cycle described in the last slide on the
given T-s diagram of R-134a.

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A few definitions

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 Tons of refrigeration
The rate of heat absorption or removal from a
system may be expressed in terms of tons of
refrigeration. One ton of refrigeration is the rate of
heat removal that is required to change the
condition of 1 ton (2000 lbm) of ice at 32oF (0oC)
to 1 ton of liquid water at 32 oF (0oC) in one day.
It comes out be 12000 Btu/hr ton = 200 Btu/min
ton = 3.5168 kW ton.

  (h1  h4 )  3.5168  N
m
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Problems [4, 1]

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Problems [4]

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Saturated table of Freon 12TM [4]

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Superheated table of Freon 12TM [4]

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Superheated table of Freon 12TM [4]

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p-h diagram of Freon 12TM [4]

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Values of gas constant (R) in various units
8314.34 m3 Pa kmol K
8.31434 m3 Pa mol K
0.00831434 m3 kPa mol K
83.1434 cm3 bar mol K
0.0000831434 m3 bar mol K
10.731 ft3 psia lbmol °R
8.31434 J mol K
0.00831434 kJ mol K
1.9872 BTU lbmol °R

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 References
[1] Cengel, Y. A.; Boles. M.A. 2006. Thermodynamics: An engineering
approach. 5th ed. McGraw-Hill.
[2] Ott, J.B., Boerio-Goates, J. 2000. Chemical thermodynamics: Principles and
Applications. reaction engineering. Elsevier.
[3] Himmelblau, D.M. 2004. Basic principles and calculations in chemical
engineering. 7th ed. Prentice-Hall.
[4] Mark, M.; Foster, A.R. 1979. Thermodynamics: Principles and Applications.
Allyn and Bacon, Inc., Sydney.

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