Chemical Engineering

Thermodynamics

Turbojet with afterburner

SCME, NUST
Questions, complaints, remarks, suggestions
• Finally: questions, suggestions, remarks and
complaints, please let me know!
• I can try to do something on it

• What is Thermodynamics and where do you meet it?

• What can you solve or calculate with it?

Introduction: Chemical Thermodynamics Dr. S. R. Naqvi 2

 What is Thermodynamics?
• The control of heat and fire
• Already in antiquity people could make fire / heat,
however producing work (electricity) and cold is much
more difficult
• Everything that has to do with the conversion of heat is
thermodynamics, the main theme is the study of energy
transformations (heat and power)
• From the Greece: θερμη, thermos: heat
δυναμις, dynamis: power / movement
• Temperature, density and pressure are important
parameters, they can change when work is delivered to
or by a system or when heat is supplied or removed

Thermodynamics: science using heat and power

Fire in early days

Introduction: Chemical Thermodynamics Dr. S. R. Naqvi 3

 What is Thermodynamics?

What is not a thermodynamic system?

A. Steam turbine
B. Gas turbine
C. Wind turbine
D. Refrigerator
E. Piston cylinder device

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Introduction: Chemical Thermodynamics Dr. S. R. Naqvi 4

 What is Thermodynamics?
• Everything that has to do with the conversion of heat is thermo-
dynamics, the main theme is the study of energy transformations
(heat and power)

• In a steam turbine, a gas turbine and an piston cylinder device (like a

diesel engine) heat from a fuel source is converted into work or
electricity

• In a refrigerator work / electricity is converted into cold (which is a form of

heat)
• In a wind turbine the rotation of the shaft is converted into electricity
• Here no heat is converted but the velocity of the wind is converted into
electricity

Introduction: Chemical Thermodynamics Dr. S. R. Naqvi 5

 What is Thermodynamics?
• A steam turbine, a gas turbine and an piston cylinder device are all
examples of heat engines in which heat from a heat source (e.g. fuel or
solar heat) is converted into work or electricity
Heat out
Heat in

A steam engine is an example of a heat engine, a

typical thermodynamic system. Heat form a heat
Work
source (boiler) on the left is converted into work by a
series of pistons. In a heat engine always some heat is
rejected to a heat sink (condenser).

Animation from http://en.wikipedia.org/wiki/Thermodynamics

• In a refrigerator something else happens, work / electricity is converted into

cold (which is a form of heat)
• Heat is transported in the non-spontaneous direction using work /
electricity

Introduction: Chemical Thermodynamics Dr. S. R. Naqvi 6

 What is Thermodynamics?
What is the maximum efficiency a heat engine in the
ideal world can have?
A. 100%
B. 80%
C. Depends on the amount of fuel
D. Depends on the temperature outside and the temperature of
the supplied heat
E. Non of the answers above

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Introduction: Chemical Thermodynamics Dr. S. R. Naqvi 7

 What is Thermodynamics?
• The efficiency of a heat engine in the ideal world can never be 100%
• In a heat engine always some heat has to be released to the outside
• The efficiency of a heat engine depends on the temperature of the outside
to which the heat is supplied (Tcold) and the temperature of the heat that is
supplied to the engine (Thot)
• The maximum efficiency for any heat engine operating between Thot and
Tcold is the Carnot efficiency (always smaller than 100%)

Heat out
Heat in

A steam engine is an example of a heat engine, a

typical thermodynamic system. Heat form a heat
Work
source (boiler) on the left is converted into work by a
series of pistons. In a heat engine always some heat is
rejected to a heat sink (condenser).

Animation from http://en.wikipedia.org/wiki/Thermodynamics

Introduction: Chemical Thermodynamics Dr. S. R. Naqvi 8

 What is Thermodynamics?
What is an example of a thermodynamic question
covered in this course?
A. Determination of the cooling down time of a 'bitterbal'
B. Determination of the flow around an airplane engine
C. Determination of the size of a heat exchanger
D. Determination of the amount of heat needed for a solar
tower
E. Non of the questions above

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Introduction: Chemical Thermodynamics Dr. S. R. Naqvi 9

 What is Thermodynamics?
• Everything that has to do with the conversion of heat is thermo-
dynamics, the main theme is the study of energy transformations
(heat and power)

A. Determination of the cooling down time of a meat ball 'bitterbal‘

- No conversion of heat but only cooling, subject of Heat Transfer
(module 7)

B. Determination of the flow around an airplane engine

- No conversion of heat, flow is subject of Fluid Mechanics
(module 7)

C. Determination of the size of an heat exchanger

- Exchange of heat is thermodynamics, but determination of the size is
subject of Heat Transfer (module 7)

D. Determination of the amount of heat needed for a solar tower

- Conversion of heat into work / electricity is thermodynamics

Introduction: Chemical Thermodynamics Dr. S. R. Naqvi 10

 What is Thermodynamics?

What was first?

A. Thermodynamics theory
B. Steam engine
C. Gas turbine
D. Refrigerator

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Introduction: Chemical Thermodynamics Dr. S. R. Naqvi 11

 Development of Thermodynamics
• What was first? A: Thermodynamics > 1800
theory 1712
B: Steam engine Around 1950
C: Gas turbine Beginning of 1900
D: Refrigerator
• Historically, thermodynamics developed out of the need to increase the
efficiency of early steam engines (used in the coal mines in England)

• Steam engines mark the beginning of the industrial revolution and have
therefore played an important role in the development of our modern
society

• Thermodynamics is one of the most

fundamental sciences

http://www.zaans‐industrieel‐erfgoed.nl/pages_4/rep_no_engeland_tyne.html

Introduction: Chemical Thermodynamics Dr. S. R. Naqvi 12

 What is Engineering Thermodynamics?
• Engineering Thermodynamics: application of thermodynamics to solve
technological problems that engineers face

• Analysis of transport and conversion of various forms of energy:

work ↔ electricity ↔ heat ↔ cold

• The objectives are:

1. Conversion of heat (fuel) into work / electricity (heat
engine)
2. Transportation of heat using work / electricity (cooling /
heat pump)

Heat converted into work (electricity) Heat converted into work Work (electricity) con-
to generate power verted into cold

Introduction: Chemical Thermodynamics Dr. S. R. Naqvi 13

Engineering Thermodynamics – Heat engine
1. Convert fuel / heat in work (heat engine)
• What do you want to know?
• How much net work / electricity (power) is produced
• How much heat (energy / fuel) do you have to put in
• What is the efficiency

Out Heat

In Heat / fuel

Out Net
Electricity

Introduction: Chemical Thermodynamics Dr. S. R. Naqvi 14

 Examples – Heat engine
• Installations or machines that convert fuel or heat to work or electricity
(power) using water / steam as working fluid

Introduction: Chemical Thermodynamics Dr. S. R. Naqvi 15

 Examples – Heat engine
• Installations or machines that convert fuel or heat to work or electricity
(power) using hot and compressed air as working fluid

Introduction: Chemical Thermodynamics Dr. S. R. Naqvi 16

 Engineering Thermodynamics - Cooling
2. Transportation of heat using work / electricity
(cooling / heat pump)
• What do you want to know?
• What is the cooling capacity
• How much electricity is required
• What is the coefficient of performance (COP)

Heat in

Electricity in Heat out

Introduction: Chemical Thermodynamics Dr. S. R. Naqvi 17

 Examples – Cooling / Heatpomp
• Installations or machines that transport heat using work / electricity

Introduction: Chemical Thermodynamics Dr. S. R. Naqvi 18

 1: Introduction and basic concepts
• Identify the vocabulary of thermodynamics through the
defenition of basic concepts
• Basic concepts of thermodynamics
• Systems (open, closed, isolated) and boundaries
• Properties (extensive, intensive, specific)
• States and State Postulate
• Equilibrium and quasi-equilibrium
• Processes and cycles

• Metric system and fundamental units

• Volume and density
• Temperature and the zeroth law of thermodynamics
• Pressure (absolute and gage pressure)

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2: Energy, work, heat, enthalpy, entropy
• Concept of energy and various forms of energy
• Internal, kinetic and potential energy

• State and path functions

• Mechanisms of energy transfer
• Heat and heat transfer
• Work (electrical and several forms of mechanical work)
• Flow Work (Pv)

• The rate of doing ….. (work, heat transfer, mass transfer)

• The first law of thermodynamics
• Energy balances
• Enthalpy
• Entropy
• Efficiency of energy conversion processes
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 3: Phase-change processes: Water
• Pure substances
• Physics of phase change processes
• Phase change and P - v - T surface (P-v, T-v, diagrams)
• Liquid - steam - mixture
• Saturation and quality
• Tables / diagrams to obtain
thermodynamica proporties of water
• Specific heat of water

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 4: First law of thermodynamics
• Energy balance of closed systems
• Conservation of mass and mass balances
• Flow work
• Total energy of a flowing fluid
• Energy balance of steady flow systems
• Applications of the first law of thermodynamics to
• Turbines
• Compressors
• Pumps, blowers
• Nozzles and diffusers
• Throttling valves
• Heat exchangers Air being heated in- A rocket demonstrates
• Mixing device side the cylinder some of the energy
shows energy transfer flows that can occur in
in a closed system an open system

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 5: Second law of thermodynamics
• Direction of processes
• Reversible and irreversible processes
• Entropy
• Gibb equations
• Inequality of Clausius
State 1 State 2
• Second law of thermodynamics
• Second law applied to processes
• Isentropic efficiencies

Ice cubes will melt

but will not be A spontaneous
created process will
spontaneously at always result in
room temperature more disorder

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6: Cycles for work, cold and heat, Carnot
A generic heat engine
• Processes and devices are combined to
make practical cycles (engines /
installations)
1. Heat power cycles
2. Refrigeration / heat pump cycles

• The laws of thermodynamics for cycles

• Thermal efficiency of a heat power cycle
• Carnot cycle and Carnot efficiency
• COP of refrigeration and heat pump cycles
• Kelvin-Planck and Clausius statement
• Perpetual - Motion Machines
A perpetual – motion machine, an
impossible cycle (M.C.
Escher)
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 7: Vapor power cycles, simple
• Introduce the tools that need to study real thermodynamic
systems that produce power or cold
• vapor power cycles, cycles using a working fluid that under- goes a
phase transition (mostly water) through the cycle, are studied
• Piston steam engine & steam turbine
• Ideal and real Rankine cycles
• Heat and power in- and output
• Thermal efficiency
• Comparison to Carnot (and Brayton)
• Design parameters
• Mollier diagram for water
Power generation using a vapor power cycle,
e.g. the power plant in Geertruidenberg (NL)
• Gas power cycles, cycles using gas as a
working fluid through the whole cycle will be treated later
• Refrigeration and heat pump cycles, cycles moving heat opposite to the
natural direction using power
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 8: Vapor power cycles, advanced
• Introduce the tools that need to study real thermodynamic systems
that produce power or cold
• simple vapor power cycles, cycles using a working fluid that under-
goes a phase transition (mostly water) through the cycle, were studied

• Piston steam engine & steam turbine

• Ideal and real Rankine cycles
• Heat and power in- and output
• Thermal efficiency
• Comparison to Carnot (and Brayton)
• Design parameters
Power generation using a vapor power cycle,
• Mollier diagram for water e.g. the power plant in Geertruidenberg (NL)

• we will see how to improve the efficiency by

• Reheating
• Regenerative feed water heating
• Cogeneration
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 9: Properties of gases
• Will study properties of water
• Vapor power cycles that use water

• Properties of gases
• How can we get values for air or
other gases
• Diagrams and tables
• Ideal gas law
• Internal energy for ideal gas
• Enthalpy for ideal gas
• Specific heat capacities for
gases
• Cp: for constant pressure
• Cv for constant volume Ideal gas ! Pv = RT

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 10: Gas power cycles, simple
• Gas power cycles, cycles using gas as working fluid through
the whole cycle to produce power, are studied
• Air-standard cycle
• Open and closed Brayton cycle
• Ideal and real Brayton cycle
• Heat and power in- and output
• Thermal efficiency
• Comparison to Rankine cycle
• Design parameters
• Mollier diagram for air

A basic gas turbine engine

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 11: Gas power cycles, advanced
• Simple gas power cycles, cycles using gas as working fluid through
the whole cycle to produce power, were studied

• Air-standard cycle, open and closed, ideal and real Brayton cycle
• Heat and power in- and output
• Thermal efficiency
A modern jet
• Comparison to Carnot and Rankine engine used to
power Boeing
• Design parameters 777 aircraft.
• Mollier diagram for air This is a Pratt
& Whitney
PW4084
turbofan
capable of
producing 374
kN of thrust.

• Improve the efficiency of a simple Brayton cycle by

using reheating, inter cooling and/or regeneration
• Aircraft gas turbine engines
• Combined cycles

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