The beginning

“Everything must have a beginning.”

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 Origins of thermodynamics

Question: What was the most influential invention mankind ever made?

This is a very tough

and debatable
question.

Many books have been

written to answer such
a question.

If you look at these books, you will find that STEAM ENGINE is always among the top.
Copyright Dr. Nayef M. Alsaifi, 2013
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 Origins of thermodynamics

 Questions

 What is steam engine?

 Why is steam engine one of the greatest invention?

 What has steam engine got to do with thermodynamics?

 Brief History of the Steam Engine

 The first known steam engine is the one

that was invented by Heron of Alexandria
2000 years ago.

 The principal idea of the steam engine is

to use heat energy to produce
mechanical motion.

 There is no useful practical application

of Heron’s steam engine, it could be
considered as a toy. Heron of Alexandria Heron’s steam engine
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 Origins of thermodynamics

 Heron’s steam engine

 Principal idea:
Heat Energy Mechanical motion (work)
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 Heat effects

 Familiar effects of heat:

 Evaporating a liquid
 Melting a solid (ice, for example)

 Un-familiar effect of heat:

 Heat can produce motion

(as seen in the pervious slide)

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 Steam engine

2000 years ago 1650-1715 1664-1729 1736-1819

1500 years

no improvement

Heron Thomas Savery Thomas Newcomen James Watt

no useful practical pumping water out pumping water out made

of coal mines of coal mines a revolution
application
more efficient

James Watt’s steam engine is the most efficient in producing useful work from heat.
(converting heat to useful work)
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 Watt’s steam engine

In 1769, James watt received a patent for his modification of Newcomen ‘s steam Engine.

James Watt (1736-1819)

 Watt’s steam engine :

 Made a great impact on the way of life for people in agriculture, manufacturing,
mining, transportation and technology
 Propelled the Industrial Revolution in Europe.

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 Steam Engine Changed the World

 If you are interested in reading about how steam engine changed the world, consult
the following article:

Steam Engine Changed the World

http://www.livescience.com/2612-steam-engine-changed-world.html

Charles Parsons' Turbinia yacht, seen Two women war workers driving a steam
here in 1897, was the first steam engine at a site for tank trials in
turbine-powered ship. Lincolnshire. (Photo by Topical Press
Agency/Getty Images). 5th March 1918
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 What has steam engine got to do with thermodynamics?

Do we really want to know the

history of steam engine to
understand thermodynamics?

The answer is of course NO. But, it will help you to remember a very
important point about the second law of thermodynamics:
Whatever you try to improve an engine (or any thermodynamic
process), there is a limit. That limit came from the second law of
thermodynamics. It is impossible to develop an engine with 100 %
efficiency. This is the main idea of the second law of
thermodynamics.

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 Another look at Steam Engine

 In 1824, Sadi Carnot, a brilliant young engineer, looked at

the steam engine from different angle:

 Unlike previous scientists and engineers, Carnot didn’t work on

the machine parts.

 Carnot emphasised that scientists were successful to improve

steam Engine based on chance but not on theory.

Sadi Carnot (1796–1832)

 He tried to answer the following questions:

 Is there a limit of improving steam engine?

 Can we use atmospheric air instead of water vapor ?

 Carnot was the first to study steam engine THEORETICALLY. He discussed

his theory in terms of temperature, pressure and volume.

 He proved theoretically that :

HEAT CANNOT BE COMPLETELY CONVERTED TO WORK

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11
 The second law of thermodynamics

 As a result of Carnot's work, Clausius and Kelvin formulated

the second law of thermodynamics.

 The second law of thermodynamics could be stated as follows:

“It is impossible to take heat from a hot reservoir and

convert it completely into work by a cyclic process
without transferring a part of it to a cold reservoir.”

Rudolf Clausius (1822-1888)

 Clausius had represented the second law of thermodynamics

mathematically.

 From the second law of thermodynamics a state function

called entropy (S) was defined.

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 First law of thermodynamics

 Besides, the work of the second law of thermodynamics, there

was extensive work that had been carried out on the amount of
energy and its transformation.

 The work on the amount of energy and its transformation had

long history. The foundation of the law of energy amount is
credited to many scientists like Mayer, Joule and Helmholtz.
Their effort had contributed to the foundation of the first law of
thermodynamics. Julius Robert von Mayer
1814-1878

 The first law of thermodynamic could be stated

as follows:

“Energy is conserved and it can be neither created

nor destroyed, but it can only be transformed into
other types”

Hermann von Helmholtz

1821-1894  From the first law of thermodynamics a state James Joule
function called internal energy (U) was defined. 1818-1889
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 Foundation of thermodynamics

 Clausius brought together the first and second laws and built the
foundations of thermodynamics.

 Kelvin was the first to call it thermodynamics where:

thermo means heat and dynamics means power or strength.
Therefore, thermodynamic mean:

the power of heat. Rudolf Clausius (1822-1888)

 The name found widespread acceptance and was used from that time
till now. It is clear that at that time thermodynamics was the science of
heat engines.

 Later, it was found that the applications of the combination of the

first and the second laws (i.e. thermodynamics) are not limited to
heat engines but they could be used in many very useful applications
and in almost all sciences.
Lord Kelvin (1824-1907)

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 Foundation of thermodynamics

 Therefore, thermodynamics was mainly established based on the combination of two

fundamental laws:

First law of thermodynamics Second law of thermodynamics

 Nowadays, thermodynamics could be defined as follows:

Thermodynamics is the physical science that deals with the study of energy,
energy transformations and its relation to matter.

 The fist law of thermodynamics is about the conservation of energy. Energy can
change from one form to another but the total amount of energy remains always
constant.

 The second law of thermodynamics could be stated as “The complete

conversion of heat into work is impossible without leaving some effect
elsewhere.”. It can equivalently be stated as “Heat does not spontaneously
flow from a cold body to a hot body *”.

* This statement might look different from the first statement but if you understand the second law clearly,
you will figure out that they are equivalent.
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 Zeroth Law of Thermodynamics

 At the beginning of the twentieth century, another law had been added. This law is related
to temperature which is a central property in thermodynamics.
 First formulated by R.H. Fowler in 1931

 The Zeroth law of thermodynamics can be stated as:

“If object A is in thermal equilibrium with object B, and object B is in thermal
equilibrium with object C, then object C is also in thermal equilibrium with object A”

Thermometer
C

Object
Object B
A

 The Zeroth law is a result of thermal equilibrium.

 It indicates that temperature is a well-defined physical quantity.

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 Results of the zeroth, first and second laws

Resulting function
of state
 Zeroth law of thermodynamics Temperature (T)

 First law of thermodynamics Internal energy (U)

 Second law of thermodynamics Entropy (S)

What does LAW mean?

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 Different equivalent definitions of thermodynamics

 Thermodynamics can be defined as:

 Thermodynamics is the study of energy, energy transformations and

its relation to matter.

 Thermodynamics is the science that deals with the relationship of

heat and mechanical energy and conversion of one into the
other.

 Thermodynamics is a theory which gives us a set of relations

between macroscopic properties we can measure such as
temperature, pressure and volume.

The last definition might look different but it is indirectly equivalent to the
first two definitions.

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 Why do we need to study chemical Engineering thermodynamics?

 The purpose of chemical engineering thermodynamics is:

 To determine the feasibility of processes

 To utilize energy efficiently

 To calculate thermal-physical properties

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 Thermodynamic vocabulary

"Every science requires a special language because every

science has its own ideas."

Étienne Bonnot de Condillac, French philosopher

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 System, Boundary & Surroundings

System: the part of the universe under study.

Boundary: the surface bounding the system.

S u r r o u n d i n g s : the part of the universe outside the boundary.

Boundary
System
(usually fluids)

Surroundings

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 Thermodynamic systems

An isolated system: A system that doesn't exchange ENERGY (i.e. work or heat)
or MATTER with its surroundings.

A closed system: A system that exchanges ENERGY with the surroundings but
doesn't exchange MATTER.

An open system: A system that exchanges both ENERGY and MATTER

with its surroundings.

An isolated system A closed system An open system

 Thermodynamic properties

 Temperature, pressure, energy, entropy, density, molar volume, etc. are

called thermodynamic properties

 Thermodynamic properties can be classified as intensive and extensive:

 Intensive properties: independent of the mass like pressure,

temperature and density

 Extensive properties: dependent of the mass (their values

change with change in mass) like volume,
energy and entropy.

Important !
A thermodynamic property is a point (or state) function NOT a path function.
However, work and heat are path functions

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 Thermodynamic state of a system

In daily life In thermodynamics

How is his condition (state)? Is he sick?

System

Butane
Gas

To determine his condition: In thermodynamics, to understand

We specify his condition by systems, we also specify the state of the
temperature, pressure, etc. system with temperature, pressure,
Then, we can talk about his condition volume, etc.
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 Thermodynamic state of a system

 State of the system is the condition of the system which can be specified by pressure,
temperature, volume, density, energy etc.

 Examples:
State 1 State 2

gas gas
T1 =450 K T2 =500 K
P1=2 atm P2=2 atm

This is a state This is another state

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 Thermodynamic state of a system

 Before studying any thermodynamic system, it is very important to

to answer the following two questions:

 How many thermodynamic properties do we need to specify

thermodynamic state of a system?

 How do we know which properties to choose?

The above two questions will be explored later in this course.

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 Processes

When a thermodynamic system changes from one state to another state

, we said that the system undergoes (executes) a process.

Different categories of processes

 Isothermal process: constant temperature process.

Temperature = 300 K Temperature = 300 K

Pressure = 10 atm Pressure = 5 atm

Thermodynamic State 1 Thermodynamic State 2

 Isobaric process : constant pressure process.
 Isometric process: constant volume process
 adiabatic process : heat doesn't cross the system boundary
 Reversible process (ideal process): the initial state of the system can be
restored with no observable effects in the system and its surroundings.
 Irreversible process (real process): the initial state of the system can be
restored without observable effects in the system and its surroundings.
 cyclic process a process in which the initial and final states are identical
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 Processes

Important !
The states that define a thermodynamic process must be in equilibrium
(system variables such as temperature and pressure don’t change with time)

Equilibrium: a condition in which the thermodynamic state doesn't

change with time and doesn’t have a tendency to change spontaneously .

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Question 1

 Steam Engine converts work to heat:

A. True
B. False

29
Question 2

 Cars, airplanes and ships etc. can move because

of the energy of heat.

A. True
B. False

30
 HEAT CANNOT BE COMPLETELY CONVERTED TO WORK

Example:

Heat
10000 KJ 10000 KJ
Engine*
HEAT WORK

impossible
*Heat engine is a general name of the machine that converts heat to work.
Steam engine is an example from heat engine. Steam engine uses water vapor. 31
 A car has been manufactured to take its heat from sun (solar
energy), The manufactured company claims that the car could
convert the solar energy completely into mechanical motion.
What do you think about this claim?
A. This is true during sunny days.

B. True if the engine has been designed carefully.

C. This claim is not true.

32
 THERMODYNAMICS IS TWO LAWS AND A
LITTLE MATHEMATICS

This statement doesn't indicate that the Zeroth law of thermodynamics has no
value. Actually, temperature is a very central property in thermodynamics and
Zeroth law implies that we can define the temperature.

33
 Thermodynamics is two laws and a little mathematics

 Thermodynamics was established based on the first and the second laws. Based
on the these two laws, four fundamental equations were obtained. From these
four equations, thousands of equations could be derived.

Two laws Four fundamental equations Thousands of equations

 Most of the thousands equations have little use. However, some are very useful in
describing the properties of chemical systems in terms of thermodynamic
variables.

 What do you mean by “properties” and “thermodynamic variables”?

 To understand any science, we must first learn its language. Therefore, we must
first learn THE LANGUAGE OF THERMODYNAMICS.

34
 Examples

Question 3

 If you consider the water in the kettle as the system, do you think it is

(A) A closed system

(B) An open system

(C) An isolated system

35
 Examples

Question 4
insulator

 If you consider the oil in the thermos as the system, do you think it is
(A) A closed system
(B) An open system

(C) An isolated system

36
 Examples

Question 5 gas

 If you consider the gas in the tank as a system, do you think it is

(A) A closed system
(B) An open system

(C) An isolated system

37
Question 6

vapor

liquid

vapor

liquid

 If you consider the vapor and liquid (specified by the red dot-line) as a
system, do you think it is
(A) A closed system
(B) An open system

(C) An isolated system

38
 Question 7

vapor

liquid

vapor

liquid

 If you consider the liquid (specified by the red dot-line) as a system, do

you think it is

(A) A closed system

(B) An open system
(C) An isolated system
39
 Question 8

vapor

liquid

vapor

liquid

 If you consider the vapor and liquid in the two tanks (specified by the red dot-line)
as a system, do you think it is

(A) A closed system

(B) An open system

(C) An isolated system

40
Question 9

 What is specific volume?

(A) Volume /mass

(B) Volume

(C) Volume/mole

41
Question 10

 What is specific internal energy?

(A) Internal energy/mass

(B) Internal Energy

(C) Internal Energy/mole

42
Question 11

 What is molar volume?

(A) Volume /mass
(B) Volume
(C) Volume/mole

43
 Thermodynamic properties

Question 12

 Which one is NOT intensive property?

(A) Specific entropy

(B) Molar internal energy

(C) Mole

(D) Molar volume

(E) density

44
Answers to practice questions:
(1) B
(2) A
(3) B
(4) C
(5) B
(6) B
(7) B
(8) A
(9) A
(10)A
(11) C
(12)C

45
 Thermodynamic properties

Question 1

 Which one is NOT intensive property?

(A) Specific entropy

(B) Molar internal energy

(C) Mole

(D) Molar volume

(E) density

46
 Thermodynamic properties

 Important !

 It is important to know the difference between state and

path functions.

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 From A to B through two different paths

Path 2 Path 1
Height = 200 m Distance traveled =
Distance traveled = 610 m
220 m

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A 48
 Thermodynamic properties

 Height (like thermodynamic property) is a point (state) function.

 Distance (like heat and work) is a path function.

 Therefore, properties such as pressure and temperature are not

dependent on the path. The change of these properties depend
only on the initial and final states of the system.

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 Chemical thermodynamics vs. Mechanical thermodynamics

Mechanical engineering thermodynamic books look simpler than chemical

Engineering thermodynamic books. Can we replace or study from a mechanical
Engineering thermodynamic books?

 The principles are the same but applications, covered topics

and viewpoints are different.

 Mechanical engineering thermodynamics generally focuses

on devices treating pure substances such as steam power plant,
refrigerators, heating systems and internal combustion engines.

 Chemical engineering thermodynamics generally focuses on

devices treating mixtures such as distillation, extraction and
rectors.

 Basic Mechanical engineering calculations need tables like steam tables.

 For mixtures, tables are not available. This is why chemical engineers
focus on theoretical models to obtain data. 50