Thermodynamics: Thermodynamics Is A Branch of Physics Concerned With Heat and
Thermodynamics: Thermodynamics Is A Branch of Physics Concerned With Heat and
Thermodynamics: Thermodynamics Is A Branch of Physics Concerned With Heat and
Contents
Introduction
History
Etymology
Branches of thermodynamics
Classical thermodynamics
Statistical mechanics
Chemical thermodynamics
Treatment of equilibrium
Laws of thermodynamics
System models
States and processes
Instrumentation
Conjugate variables
Potentials
Applied fields
See also
Lists and timelines
Wikibooks
References
Further reading
External links
Introduction
A description of any thermodynamic system employs the four laws of thermodynamics that form an axiomatic basis. The first law
specifies that energy can be exchanged between physical systems as heat and work.[12] The second law defines the existence of a
quantity called entropy, that describes the direction, thermodynamically
, that a system can evolve and quantifies the state of order of a
[13]
system and that can be used to quantify the useful work that can be extracted from the system.
In thermodynamics, interactions between large ensembles of objects are studied and categorized. Central to this are the concepts of
the thermodynamic system and its surroundings. A system is composed of particles, whose average motions define its properties, and
those properties are in turn related to one another through equations of state. Properties can be combined to express internal energy
and thermodynamic potentials, which are useful for determining conditions forequilibrium and spontaneous processes.
With these tools, thermodynamics can be used to describe how systems respond to changes in their environment. This can be applied
to a wide variety of topics in science and engineering, such as engines, phase transitions, chemical reactions, transport phenomena,
and even black holes. The results of thermodynamics are essential for other fields ofphysics and for chemistry, chemical engineering,
aerospace engineering, mechanical engineering, cell biology, biomedical engineering, materials science, and economics, to name a
few.[14][15]
This article is focused mainly on classical thermodynamics which primarily studies systems in thermodynamic equilibrium. Non-
equilibrium thermodynamics is often treated as an extension of the classical treatment, but statistical mechanics has brought many
advances to that field.
History
The history of thermodynamics as a scientific discipline generally begins with Otto von Guericke who, in 1650, built and designed
the world's first vacuum pump and demonstrated a vacuum using his Magdeburg hemispheres. Guericke was driven to make a
vacuum in order to disprove Aristotle's long-held supposition that 'nature abhors a vacuum'. Shortly after Guericke, the English
physicist and chemist Robert Boyle had learned of Guericke's designs and, in 1656, in coordination with English scientist Robert
Hooke, built an air pump.[17] Using this pump, Boyle and Hooke noticed a correlation between pressure, temperature, and volume. In
time, Boyle's Law was formulated, which states that pressure and volume are inversely proportional. Then, in 1679, based on these
concepts, an associate of Boyle's named Denis Papin built a steam digester, which was a closed vessel with a tightly fitting lid that
confined steam until a high pressure was generated.
Later designs implemented a steam release valve that kept the machine from exploding. By watching the valve rhythmically move up
and down, Papin conceived of the idea of a piston and a cylinder engine. He did not, however, follow through with his design.
Nevertheless, in 1697, based on Papin's designs, engineer Thomas Savery built the first engine, followed by Thomas Newcomen in
1712. Although these early engines were crude and inef
ficient, they attracted the attention of the leading scientists of the time.
The fundamental concepts of heat capacity and latent heat, which were necessary for the development of thermodynamics, were
developed by Professor Joseph Black at the University of Glasgow, where James Watt was employed as an instrument maker. Black
and Watt performed experiments together, but it was Watt who conceived the idea of the external condenser which resulted in a large
[18]
increase in steam engine efficiency.[18] Drawing
on all the previous work led Sadi Carnot, the
"father of thermodynamics", to publish
Reflections on the Motive Power of Fire (1824), a
discourse on heat, power, energy and engine
efficiency. The book outlined the basic energetic
relations between the Carnot engine, the Carnot
cycle, and motive power. It marked the start of
thermodynamics as a modern science.[10]
Etymology
The etymology of thermodynamics has an intricate history.[21] It was first spelled in a hyphenated form as an adjective (thermo-
[21]
dynamic) and from 1854 to 1868 as the nounthermo-dynamics to represent the science of generalized heat engines.
American biophysicist Donald Haynie claims that thermodynamics was coined in 1840 from the Greek root θέρμη therme, meaning
heat and δύναμις dynamis, meaning power.[22] However, this etymology has been cited as unlikely.[21]
Pierre Perrot claims that the term thermodynamics was coined by James Joule in 1858 to designate the science of relations between
heat and power,[10] however, Joule never used that term, but used instead the term perfect thermo-dynamic engine in reference to
Thomson’s 1849[23] phraseology.[21]
By 1858, thermo-dynamics, as a functional term, was used in William Thomson's paper "An Account of Carnot's Theory of the
Motive Power of Heat."[23]
Branches of thermodynamics
The study of thermodynamical systems has developed into several related branches, each using a different fundamental model as a
theoretical or experimental basis, or applying the principles to varying types of systems.
Classical thermodynamics
Classical thermodynamics is the description of the states of thermodynamic systems at near-equilibrium, that uses macroscopic,
measurable properties. It is used to model exchanges of energy, work and heat based on the laws of thermodynamics. The qualifier
classical reflects the fact that it represents the first level of understanding of the subject as it developed in the 19th century and
describes the changes of a system in terms of macroscopic empirical (large scale, and measurable) parameters. A microscopic
interpretation of these concepts was later provided by the development ofstatistical mechanics.
Statistical mechanics
Statistical mechanics, also called statistical thermodynamics, emerged with the development of atomic and molecular theories in the
late 19th century and early 20th century, and supplemented classical thermodynamics with an interpretation of the microscopic
interactions between individual particles or quantum-mechanical states. This field relates the microscopic properties of individual
atoms and molecules to the macroscopic, bulk properties of materials that can be observed on the human scale, thereby explaining
classical thermodynamics as a natural result of statistics, classical mechanics, and
quantum theory at the microscopic level.
Thermodynamics navigation
Chemical thermodynamics image.svg
Chemical thermodynamics is the study of the interrelation of energy with chemical
reactions or with a physical change of state within the confines of the laws of
thermodynamics.
Treatment of equilibrium
Equilibrium thermodynamics is the systematic study of transformations of matter
and energy in systems as they approach equilibrium. The word equilibrium implies a
state of balance. In an equilibrium state there are no unbalanced potentials, or
driving forces, within the system. A central aim in equilibrium thermodynamics is:
given a system in a well-defined initial state, subject to accurately specified
constraints, to calculate what the state of the system will be once it has reached
equilibrium.
Laws of thermodynamics
Thermodynamics is principally based on a set of four laws which are universally valid when applied to systems that fall within the
constraints implied by each. In the various theoretical descriptions of thermodynamics these laws may be expressed in seemingly
differing forms, but the most prominent formulations are the following:
Zeroth law of thermodynamics: If two systems are each in thermal equilibrium with a third, they are also in thermal
equilibrium with each other.
This statement implies that thermal equilibrium is an equivalence relation on the set of thermodynamic systems under consideration.
Systems are said to be in equilibrium if the small, random exchanges between them (e.g. Brownian motion) do not lead to a net
change in energy. This law is tacitly assumed in every measurement of temperature. Thus, if one seeks to decide if two bodies are at
the same temperature, it is not necessary to bring them into contact and measure any changes of their observable properties in
time.[24] The law provides an empirical definition of temperature and justification for the construction of practical thermometers.
The zeroth law was not initially recognized as a law, as its basis in thermodynamical equilibrium was implied in the other laws. The
first, second, and third laws had been explicitly stated prior and found common acceptance in the physics community. Once the
importance of the zeroth law for the definition of temperature was realized, it was impracticable to renumber the other laws, hence it
was numbered the zeroth law.
The first law is usually formulated by saying that the change in the internal energy of a closed thermodynamic system is equal to the
difference between the heat supplied to the system and the amount of work done by the system on its surroundings. It is important to
note that internal energy is a state of the system (see Thermodynamic state) whereas heat and work modify the state of the system. In
other words, a change of internal energy of a system may be achieved by any combination of heat and work added or removed from
the system as long as those total to the change of internal energy. The manner by which a system achieves its internal energy is path
independent.
Second law of thermodynamics: Heat cannot spontaneously flow from a colder location to a hotter location.
The second law of thermodynamics is an expression of the universal principle of decay observable in nature. The second law is an
observation of the fact that over time, differences in temperature, pressure, and chemical potential tend to even out in a physical
system that is isolated from the outside world. Entropy is a measure of how much this process has progressed. The entropy of an
isolated system which is not in equilibrium will tend to increase over time, approaching a maximum value at equilibrium. However,
principles guiding systems that are far from equilibrium are still debatable. One of such principles is the maximum entropy
production principle.[26][27] It states that non-equilibrium systems behave such a way as to maximize its entropy production.
[28]
In classical thermodynamics, the second law is a basic postulate applicable to any system involving heat energy transfer; in statistical
thermodynamics, the second law is a consequence of the assumed randomness of molecular chaos. There are many versions of the
second law, but they all have the same effect, which is to explain the phenomenon ofirreversibility in nature.
Third law of thermodynamics: As a system approaches absolute zero, all processes cease and the entropy of the
system approaches a minimum value.
The third law of thermodynamics is a statistical law of nature regarding entropy and the impossibility of reaching absolute zero of
temperature. This law provides an absolute reference point for the determination of entropy. The entropy determined relative to this
point is the absolute entropy. Alternate definitions are, "the entropy of all systems and of all states of a system is smallest at absolute
zero," or equivalently "it is impossible to reach the absolute zero of temperature by any finite number of processes".
Absolute zero, at which all activity would stop if it were possible to happen, is −273.15 °C (degrees Celsius), or −459.67 °F (degrees
Fahrenheit) or 0 K (kelvin).
System models
An important concept in thermodynamics is the thermodynamic system, which is a precisely defined region of the universe under
study. Everything in the universe except the system is called the surroundings. A system is separated from the remainder of the
universe by a boundary which may be a physical boundary or notional, but which by convention defines a finite volume. Exchanges
of work, heat, or matter between the system and the surroundings take place across this boundary
.
In practice, the boundary of a system is simply an imaginary dotted line drawn around a
volume within which is going to be a change in the internal energy of that volume.
Anything that passes across the boundary that effects a change in the internal energy of
the system needs to be accounted for in the energy balance equation. The volume can be
the region surrounding a single atom resonating energy, such as Max Planck defined in
1900; it can be a body of steam or air in a steam engine, such as Sadi Carnot defined in
1824; it can be the body of a tropical cyclone, such as Kerry Emanuel theorized in 1986
in the field of atmospheric thermodynamics; it could also be just one nuclide (i.e. a
system of quarks) as hypothesized in quantum thermodynamics, or the event horizon of
a black hole. A diagram of a generic
thermodynamic system
Boundaries are of four types: fixed, movable, real, and imaginary. For example, in an
engine, a fixed boundary means the piston is locked at its position, within which a
constant volume process might occur. If the piston is allowed to move that boundary is movable while the cylinder and cylinder head
boundaries are fixed. For closed systems, boundaries are real while for open systems boundaries are often imaginary. In the case of a
jet engine, a fixed imaginary boundary might be assumed at the intake of the engine, fixed boundaries along the surface of the case
and a second fixed imaginary boundary across the exhaust nozzle.
Generally, thermodynamics distinguishes three classes of systems, defined in terms of what is allowed to cross their boundaries:
As time passes in an isolated system, internal differences of pressures, densities, and temperatures tend to even out. A system in
which all equalizing processes have gone to completion is said to be in state
a of thermodynamic equilibrium.
Once in thermodynamic equilibrium, a system's properties are, by definition, unchanging in time. Systems in equilibrium are much
simpler and easier to understand than are systems which are not in equilibrium. Often, when analysing a dynamic thermodynamic
process, the simplifying assumption is made that each intermediate state in the process is at equilibrium, producing thermodynamic
processes which develop so slowly as to allow each intermediate step to be an equilibrium state and are said to be reversible
processes.
A thermodynamic processmay be defined as the energetic evolution of a thermodynamic system proceeding from an initial state to a
final state. It can be described by process quantities. Typically, each thermodynamic process is distinguished from other processes in
energetic character according to what parameters, such as temperature, pressure, or volume, etc., are held fixed. Furthermore, it is
useful to group these processes into pairs, in which each variable held constant is one member ofconjugate
a pair.
Several commonly studied thermodynamic processes are:
Instrumentation
There are two types of thermodynamic instruments, the meter and the reservoir. A thermodynamic meter is any device which
measures any parameter of a thermodynamic system. In some cases, the thermodynamic parameter is actually defined in terms of an
idealized measuring instrument. For example, the zeroth law states that if two bodies are in thermal equilibrium with a third body,
they are also in thermal equilibrium with each other. This principle, as noted by James Maxwell in 1872, asserts that it is possible to
measure temperature. An idealized thermometer is a sample of an ideal gas at constant pressure. From the ideal gas law pV=nRT, the
volume of such a sample can be used as an indicator of temperature; in this manner it defines temperature. Although pressure is
defined mechanically, a pressure-measuring device, called a barometer may also be constructed from a sample of an ideal gas held at
a constant temperature. Acalorimeter is a device which is used to measure and define the internal ener
gy of a system.
A thermodynamic reservoir is a system which is so large that its state parameters are not appreciably altered when it is brought into
contact with the system of interest. When the reservoir is brought into contact with the system, the system is brought into equilibrium
with the reservoir. For example, a pressure reservoir is a system at a particular pressure, which imposes that pressure upon the system
to which it is mechanically connected. The Earth's atmosphere is often used as a pressure reservoir. If ocean water is used to cool a
power plant, the ocean is often a temperature reservoir in the analysis of the power plant cycle.
Conjugate variables
The central concept of thermodynamics is that of energy, the ability to do work. By the First Law, the total energy of a system and its
surroundings is conserved. Energy may be transferred into a system by heating, compression, or addition of matter, and extracted
from a system by cooling, expansion, or extraction of matter. In mechanics, for example, energy transfer equals the product of the
force applied to a body and the resulting displacement.
Conjugate variables are pairs of thermodynamic concepts, with the first being akin to a "force" applied to some thermodynamic
system, the second being akin to the resulting "displacement," and the product of the two equalling the amount of energy transferred.
The common conjugate variables are:
Potentials
Thermodynamic potentials are different quantitative measures of the stored energy in a system. Potentials are used to measure the
energy changes in systems as they evolve from an initial state to a final state. The potential used depends on the constraints of the
system, such as constant temperature or pressure. For example, the Helmholtz and Gibbs energies are the energies available in a
system to do useful work when the temperature and volume or the pressure and temperature are fixed, respectively
.
Internal energy
Enthalpy
where is the temperature, the entropy, the pressure, the volume, the chemical potential, the number of particles in the
system, and is the count of particles types in the system.
Thermodynamic potentials can be derived from the energy balance equation applied to a thermodynamic system. Other
thermodynamic potentials can also be obtained throughLegendre transformation.
Applied fields
Atmospheric thermodynamics Maximum entropy thermodynamics
Biological thermodynamics Non-equilibrium thermodynamics
Black hole thermodynamics Philosophy of thermal and statistical physics
Chemical thermodynamics Psychrometrics
Classical thermodynamics Quantum thermodynamics
Equilibrium thermodynamics Statistical thermodynamics
Industrial ecology (re: Exergy) Thermoeconomics
See also
Wikibooks
Engineering Thermodynamics
Entropy for Beginners
References
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'Theory of Heat'. Poggendorff's Annalen der Physik, LXXIX (Dover Reprint).ISBN 0-486-59065-8.
2. William Thomson, LL.D. D.C.L., F.R.S. (1882). Mathematical and Physical Papers(https://books.google.com/books?i
d=nWMSAAAAIAAJ&pg=PA100&dq=On+an+Absolute+Thermometric+Scale+Founded+on+Carnot%E2%80%99s+T
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University Press. p. 232.
3. Gibbs, Willard, J. (1876).Transactions of the Connecticut Academy, III, pp. 108-248, Oct. 1875-May 1876, and pp.
343-524, May 1877-July 1878.
4. Duhem, P.M.M. (1886). Le Potential Thermodynamique et ses Applications
, Hermann, Paris.
5. Lewis, Gilbert N.; Randall, Merle (1923).Thermodynamics and the Free Energy of Chemical Substances
. McGraw-
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7. Guggenheim, E.A. (1949/1967).Thermodynamics. An Advanced Treatment for Chemists and Physicists, 1st edition
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Co., London. Includes classical non-equilibrium thermodynamics.
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(https://www.worldcat.org/oclc/123283342).
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OCLC 58732844 (https://www.worldcat.org/oclc/58732844).
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OCLC 8846081 (https://www.worldcat.org/oclc/8846081).
13. Dugdale, J.S. (1998). Entropy and its Physical Meaning. Taylor and Francis. ISBN 0-7484-0569-0. OCLC 36457809
(https://www.worldcat.org/oclc/36457809).
14. Smith, J.M.; Van Ness, H.C.; Abbott, M.M. (2005). Introduction to Chemical Engineering Thermodynamics
. McGraw
Hill. ISBN 0-07-310445-0. OCLC 56491111 (https://www.worldcat.org/oclc/56491111).
15. Haynie, Donald, T. (2001). Biological Thermodynamics. Cambridge University Press.ISBN 0-521-79549-4.
OCLC 43993556 (https://www.worldcat.org/oclc/43993556).
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17. Partington, J.R. (1989). A Short History of Chemistry. Dover. OCLC 19353301 (https://www.worldcat.org/oclc/193533
01).
18. The Newcomen engine was improved from 1711 until W att's work, making the efficiency comparison subject to
qualification, but the increase from the 1865 version was on the order of 100%.
19. Cengel, Yunus A.; Boles, Michael A. (2005).Thermodynamics - an Engineering Approach. McGraw-Hill. ISBN 0-07-
310768-9.
20. Gibbs, Willard (1993). The Scientific Papers of J. Willard Gibbs, Volume One: Thermodynamics. Ox Bow Press.
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22. Donald T. Haynie (2008). Biological Thermodynamics(2 ed.). Cambridge University Press. p. 26.
23. Kelvin, William T. (1849) "An Account of Carnot's Theory of the Motive Power of Heat - with Numerical Results
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2.Scanned Copy (http://visualiseur.bnf.fr/Visualiseur?Destination=Gallica&O=NUMM-95118)
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Further reading
Goldstein, Martin & Inge F. (1993). The Refrigerator and the Universe. Harvard University Press.ISBN 0-674-75325-
9. OCLC 32826343. A nontechnical introduction, good on historical and interpretive matters.
Kazakov, Andrei; Muzny, Chris D.; Chirico, Robert D.; Diky, Vladimir V.; Frenkel, Michael (2008)."Web Thermo
Tables - an On-Line Version of the TRC Thermodynamic T ables". Journal of Research of the National Institute of
Standards and Technology. 113 (4): 209–220. doi:10.6028/jres.113.016. ISSN 1044-677X. PMC 4651616 .
Bejan, Adrian (2016). Advanced Engineering Thermodynamics(4 ed.). Wiley. ISBN 978-1-119-05209-8.
Cengel, Yunus A., & Boles, Michael A. (2002). Thermodynamics - an Engineering Approach. McGraw Hill. ISBN 0-
07-238332-1. OCLC 45791449.
Dunning-Davies, Jeremy (1997).Concise Thermodynamics: Principles and Applications
. Horwood Publishing.
ISBN 1-8985-6315-2. OCLC 36025958.
Kroemer, Herbert & Kittel, Charles (1980).Thermal Physics. W. H. Freeman Company. ISBN 0-7167-1088-9.
OCLC 32932988.
External links
Thermodynamics Data & Property Calculation Websites
Thermodynamics Educational Websites
Thermodynamics at ScienceWorld
Biochemistry Thermodynamics
Thermodynamics and Statistical Mechanics
Engineering Thermodynamics - A Graphical Approach
Thermodynamics and Statistical Mechanicsby Richard Fitzpatrick
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