Booklet

KING FAHD UNIVERSITY OF PETROLEUM & MINERALS ADVANCED CHEMICAL ENGINEERING THERMODYNAMICS CHE-513 INSTRUCTOR: Dr. NAYEF M. ALSAIFI Pre-introduction: thermodynamic origins and Copyright Dr. Nayef M. Alsaifi, 2013 vocabulary All rights reserved
KING FAHD UNIVERSITY OF PETROLEUM   MINERALS  ADVANCED CHEMICAL ENGINEERING THERMODYNAMICS CHE-513  INSTRUCTOR  Dr. NAYEF ...
The beginning “Everything must have a beginning.” Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 2
The beginning    Everything must have a beginning.     Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved  2
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 All rights reserved
Origins of thermodynamics Question   What was the most influential invention mankind ever made  This is a very tough and d...
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. Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved Heron of Alexandria Heron’s steam engine 4
Origins of thermodynamics     Questions     What is steam engine       Why is steam engine one of the greatest invention  ...
Origins of thermodynamics  Heron’s steam engine  Principal idea: Heat Energy Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved Mechanical motion (work) 5
Origins of thermodynamics      Heron   s steam engine      Principal idea  Heat Energy Copyright Dr. Nayef M. Alsaifi, 201...
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) Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 6
Heat effects      Familiar effects of heat      Evaporating a liquid     Melting a solid  ice, for example       Un-famili...
Steam engine 2000 years ago 1650-1715 1664-1729 1736-1819 Thomas Savery Thomas Newcomen James Watt 1500 years no improvement Heron no useful practical application pumping water out pumping water out of coal mines of coal mines made a revolution more efficient James Watt’s steam engine is the most efficient in producing useful work from heat. (converting heat to useful work) Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 7
Steam engine 2000 years ago  1650-1715  1664-1729  1736-1819  Thomas Savery  Thomas Newcomen  James Watt  1500 years  no i...
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. Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 8
Watt   s steam engine In 1769, James watt received a patent for his modification of Newcomen    s steam Engine.  James Wat...
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 here in 1897, was the first steam turbine-powered ship. Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved Two women war workers driving a steam engine at a site for tank trials in Lincolnshire. (Photo by Topical Press Agency/Getty Images). 5th March 1918 9
Steam Engine Changed the World     If you are interested in reading about how steam engine changed the world, consult the ...
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. Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 10
What has steam engine got to do with thermodynamics   Do we really want to know the history of steam engine to understand ...
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 Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 11
Another look at Steam Engine     In 1824, Sadi Carnot, a brilliant young engineer, looked at the steam engine from differe...
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. Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 12
The second law of thermodynamics      As a result of Carnot s work, Clausius and Kelvin formulated the second law of therm...
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 Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved  From the first law of thermodynamics a state function called internal energy (U) was defined. James Joule 1818-1889 13
First law of thermodynamics     Besides, the work of the second law of thermodynamics, there was extensive work that had b...
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) Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 14
Foundation of thermodynamics      Clausius brought together the first and second laws and built the foundations of thermod...
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. Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 15
Foundation of thermodynamics     Therefore, thermodynamics was mainly established based on the combination of two fundamen...
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 A Object B  The Zeroth law is a result of thermal equilibrium.  It indicates that temperature is a well-defined physical quantity. Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 16
Zeroth Law of Thermodynamics     At the beginning of the twentieth century, another law had been added. This law is relate...
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? Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 17
Results of the zeroth, first and second laws Resulting function of state     Zeroth law of thermodynamics  Temperature  T ...
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. Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 18
Different equivalent definitions of thermodynamics     Thermodynamics can be defined as      Thermodynamics is the study o...
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 Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved
Why do we need to study chemical Engineering thermodynamics       The purpose of chemical engineering thermodynamics is   ...
Thermodynamic vocabulary "Every science requires a special language because every science has its own ideas." Étienne Bonnot de Condillac, French philosopher Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 20
Thermodynamic vocabulary  Every science requires a special language because every science has its own ideas.    tienne Bon...
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 Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved
System, Boundary   Surroundings  System   the part of the universe under study.  Boundary   the surface bounding the syste...
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: An isolated system A system that exchanges both ENERGY and MATTER with its surroundings. A closed system An open system
Thermodynamic systems An isolated system   A system that doesn t exchange ENERGY  i.e. work or heat  or MATTER with its su...
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 Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 23
Thermodynamic properties     Temperature, pressure, energy, entropy, density, molar volume, etc. are called thermodynamic ...
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: We specify his condition by temperature, pressure, etc. Then, we can talk about his condition In thermodynamics, to understand systems, we also specify the state of the system with temperature, pressure, volume, etc. 24
Thermodynamic state of a system In daily life  In thermodynamics  How is his condition  state   Is he sick   System  Butan...
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 T1 =450 K P1=2 atm gas T2 =500 K P2=2 atm This is a state This is another state Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 25
Thermodynamic state of a system      State of the system is the condition of the system which can be specified by pressure...
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. Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 26
Thermodynamic state of a system      Before studying any thermodynamic system, it is very important to to answer the follo...
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 Pressure = 10 atm Temperature = 300 K 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 Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 27
Processes When a thermodynamic system changes from one state to another state , we said that the system undergoes  execute...
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 . Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 28
Processes  Important   The states that define a thermodynamic process must be in equilibrium  system variables such as tem...
Question 1  Steam Engine converts work to heat: A. True B. False 29
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
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: 10000 KJ HEAT Heat Engine* 10000 KJ 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
HEAT CANNOT BE COMPLETELY CONVERTED TO WORK Example   10000 KJ HEAT  Heat Engine   10000 KJ WORK  impossible  Heat engine ...
 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
    A car has been manufactured to take its heat from sun  solar energy , The manufactured company claims that the car cou...
THERMODYNAMICS IS TWO LAWS LITTLE MATHEMATICS AND A 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 LITTLE MATHEMATICS  AND  A  This statement doesn t indicate that the Zeroth law of thermodynami...
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
Thermodynamics is two laws and a little mathematics      Thermodynamics was established based on the first and the second ...
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 3      If you consider the water in the kettle as the system, do you think it is  A  A closed system  B...
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 4 insulator      If you consider the oil in the thermos as the system, do you think it is  A  A closed ...
Examples gas Question 5  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
Examples  gas  Question 5      If you consider the gas in the tank as a system, do you think it is  A  A closed system  B ...
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 6  vapor  liquid vapor  liquid     If you consider the vapor and liquid  specified by the red dot-line  as a syst...
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 7  vapor  liquid vapor  liquid      If you consider the liquid  specified by the red dot-line  as a system, do yo...
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 8  vapor  liquid vapor  liquid     If you consider the vapor and liquid in the two tanks  specified by the red do...
Question 9  What is specific volume? (A) Volume /mass (B) Volume (C) Volume/mole 41
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 10      What is specific internal energy   A  Internal energy mass  B  Internal Energy  C  Internal Energy mole  ...
Question 11  What is molar volume? (A) Volume /mass (B) Volume (C) Volume/mole 43
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
Thermodynamic properties  Question 12      Which one is NOT intensive property   A  Specific entropy   B  Molar internal e...
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
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  Question 1      Which one is NOT intensive property   A  Specific entropy   B  Molar internal en...
Thermodynamic properties  Important !  It is important to know the difference between state and path functions. Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 47
Thermodynamic properties      Important       It is important to know the difference between state and path functions.  Co...
From A to B through two different paths B Path 2 Height = 200 m Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved Distance traveled = 220 m A Path 1 Distance traveled = 610 m 48
From A to B through two different paths B  Path 2 Height   200 m  Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved...
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. Copyright Dr. Nayef M. Alsaifi, 2013 All rights reserved 49
Thermodynamic properties      Height  like thermodynamic property  is a point  state  function.     Distance  like heat an...
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
Chemical thermodynamics vs. Mechanical thermodynamics  Mechanical engineering thermodynamic books look simpler than chemic...