Thermodynamics

Thermodynamics (from the Greek θερμη, therme, meaning "heat" and δυναμις, dynamis, meaning "power") is a branch of physics that studies the effects of changes in temperature, pressure, and volume on physical systems at the macroscopic scale by analyzing the collective motion of their particles using statistics.<ref name="Perrot" >Perrot, Pierre (1998). A to Z of Thermodynamics. Oxford University Press. ISBN 0-19-856552-6. [1] Roughly, heat means "energy in transit" and dynamics relates to "movement"; thus, in essence thermodynamics studies the movement of energy and how energy instills movement. Historically, thermodynamics developed out of need to increase the efficiency of early steam engines.[2]
Typical thermodynamic system - heat moves from hot (boiler) to cold (condenser), (both not shown) and work is extracted, in this case by a series of pistons.
The starting point for most thermodynamic considerations are the laws of thermodynamics, which postulate that energy can be exchanged between physical systems as heat or work.[3] They also postulate the existence of a quantity named entropy, which can be defined for any system.[4] In thermodynamics, interactions between large ensembles of objects are studied and categorized. Central to this are the concepts of system and surroundings. A system is composed of particles, whose average motions define its properties, which in turn are 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 for equilibrium and spontaneous processes.

With these tools, thermodynamics describes how systems respond to changes in their surroundings. 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 of physics and for chemistry, chemical engineering, aerospace engineering, mechanical engineering, cell biology, biomedical engineering, and materials science to name a few.[5][6]

History

Sadi Carnot (1796-1832): the "father" of thermodynamics

A brief history of thermodynamics begins with Otto von Guericke who in 1650 built and designed the world's first vacuum pump and created the world's first ever vacuum (known as the Magdeburg hemispheres). He was driven to make a vacuum in order to disprove Aristotle's long-held supposition that 'nature abhors a vacuum'. Shortly thereafter, Irish 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.[7] Using this pump, Boyle and Hooke noticed the pressure-temperature-volume correlation. 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 bone 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. Although these early engines were crude and inefficient, they attracted the attention of the leading scientists of the time. One such scientist was Sadi Carnot, the "father of thermodynamics", who in 1824 published Reflections on the Motive Power of Fire, a discourse on heat, power, and engine efficiency. The paper outlined the basic energetic relations between the Carnot engine, the Carnot cycle, and Motive power. This marks the start of thermodynamics as a modern science.<ref name="Perrot" />

The term thermodynamics was coined by James Joule in 1858 to designate the science of relations between heat and power.<ref name="Perrot" /> By 1849, "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.[8] The first thermodynamic textbook was written in 1859 by William Rankine, originally trained as a physicist and a civil and mechanical engineering professor at the University of Glasgow.[9]

Classical thermodynamics

Classical thermodynamics is the original early 1800s variation of thermodynamics concerned with thermodynamic states, and properties as energy, work, and heat, and with the laws of thermodynamics, all lacking an atomic interpretation. In precursory form, classical thermodynamics derives from chemist Robert Boyle’s 1662 postulate that the pressure P of a given quantity of gas varies inversely as its volume V at constant temperature; i.e. in equation form: PV = k, a constant. From here, a semblance of a thermo-science began to develop with the construction of the first successful atmospheric steam engines in England by Thomas Savery in 1697 and Thomas Newcomen in 1712. The first and second laws of thermodynamics emerged simultaneously in the 1850s, primarily out of the works of William Rankine, Rudolf Clausius, and William Thomson (Lord Kelvin).[10]

Statistical thermodynamics

With the development of atomic and molecular theories in the late 19th century, thermodynamics was given a molecular interpretation. This field is called statistical thermodynamics, which can be thought of as a bridge between macroscopic and microscopic properties of systems.[11] Essentially, statistical thermodynamics is an approach to thermodynamics situated upon statistical mechanics, which focuses on the derivation of macroscopic results from first principles. It can be opposed to its historical predecessor phenomenological thermodynamics, which gives scientific descriptions of phenomena with avoidance of microscopic details. The statistical approach is to derive all macroscopic properties (temperature, volume, pressure, energy, entropy, etc.) from the properties of moving constituent particles and the interactions between them (including quantum phenomena). It was found to be very successful and thus is commonly used.

Chemical thermodynamics

Chemical thermodynamics is the study of the interrelation of heat with chemical reactions or with a physical change of state within the confines of the laws of thermodynamics. During the years 1873-76 the American mathematical physicist Josiah Willard Gibbs published a series of three papers, the most famous being On the Equilibrium of Heterogeneous Substances, in which he showed how thermodynamic processes could be graphically analyzed, by studying the energy, entropy, volume, temperature and pressure of the thermodynamic system, in such a manner to determine if a process would occur spontaneously.[12] During the early 20th century, chemists such as Gilbert N. Lewis, Merle Randall, and E. A. Guggenheim began to apply the mathematical methods of Gibbs to the analysis of chemical processes.[13]

Thermodynamic systems

Main article: Thermodynamic system
An important concept in thermodynamics is the “system”. Everything in the universe except the system is known as surroundings. A system is the region of the universe under study. A system is separated from the remainder of the universe by a boundary which may be imaginary or not, but which by convention delimits a finite volume. The possible exchanges of work, heat, or matter between the system and the surroundings take place across this boundary. Boundaries are of four types: fixed, moveable, real, and imaginary.

Basically, the “boundary” is simply an imaginary dotted line drawn around the volume of a something in which there is going to be a change in the internal energy of that something. Anything that passes across the boundary that effects a change in the internal energy of that something needs to be accounted for in the energy balance equation. That “something” can be the volumetric 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 some are theorizing presently in quantum thermodynamics.

For an engine, a fixed boundary means the piston is locked at its position; as such, a constant volume process occurs. In that same engine, a moveable boundary allows the piston to move in and out. For closed systems, boundaries are real while for open system boundaries are often imaginary. There are five dominant classes of systems:
1. Isolated Systems – matter and energy may not cross the boundary.
2. Adiabatic Systems – heat must not cross the boundary.
3. Diathermic Systems - heat may cross boundary.
4. Closed Systems – matter may not cross the boundary.
5. Open Systems – heat, work, and matter may cross the boundary (often called a control volume in this case).

As time passes in an isolated system, internal differences in the system tend to even out and pressures and temperatures tend to equalize, as do density differences. A system in which all equalizing processes have gone practically to completion, is considered to be in a state of thermodynamic equilibrium.

In thermodynamic equilibrium, a system's properties are, by definition, unchanging in time. Systems in equilibrium are much simpler and easier to understand than systems which are not in equilibrium. Often, when analysing a thermodynamic process, it can be assumed that each intermediate state in the process is at equilibrium. This will also considerably simplify the situation. Thermodynamic processes which develop so slowly as to allow each intermediate step to be an equilibrium state are said to be reversible processes.

Thermodynamic parameters

The central concept of thermodynamics is that of energy, the ability to do work. As stipulated by the first law, the total energy of the system and its surroundings is conserved. It may be transferred into a body by heating, compression, or addition of matter, and extracted from a body either by cooling, expansion, or extraction of matter. For comparison, in mechanics, energy transfer results from a force which causes displacement, the product of the two being the amount of energy transferred. In a similar way, thermodynamic systems can be thought of as transferring energy as the result of a generalized force causing a generalized displacement, with the product of the two being the amount of energy transferred. These thermodynamic force-displacement pairs are known as conjugate variables. The most common conjugate thermodynamic variables are pressure-volume (mechanical parameters), temperature-entropy (thermal parameters), and chemical potential-particle number (material parameters)..

Thermodynamic instruments

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. A calorimeter is a device which is used to measure and define the internal energy of a system.

A thermodynamic reservoir is a system which is so large that it does not appreciably alter its state parameters when brought into contact with the test system. It is used to impose a particular value of a state parameter upon the system. For example, a pressure reservoir is a system at a particular pressure, which imposes that pressure upon any test system that it is mechanically connected to. The earth's atmosphere is often used as a pressure reservoir.

It is important that these two types of instruments are distinct. A meter does not perform its task accurately if it behaves like a reservoir of the state variable it is trying to measure. If, for example, a thermometer, were to act as a temperature reservoir it would alter the temperature of the system being measured, and the reading would be incorrect. Ideal meters have no effect on the state variables of the system they are measuring.

Thermodynamic states

Main article: Thermodynamic state

When a system is at equilibrium under a given set of conditions, it is said to be in a definite state. The state of the system can be described by a number of intensive variables and extensive variables. The properties of the system can be described by an equation of state which specifies the relationship between these variables. State may be thought of as the instantaneous quantitative description of a system with a set number of variables held constant.

Thermodynamic processes

A thermodynamic process may be defined as the energetic evolution of a thermodynamic system proceeding from an initial state to a final state. Typically, each thermodynamic process is distinguished from other processes, in energetic character, according to what parameters, 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 of a conjugate pair. The seven most common thermodynamic processes are shown below:
1. An isobaric process occurs at constant pressure.
2. An isochoric process, or isometric/isovolumetric process, occurs at constant volume.
3. An isothermal process occurs at a constant temperature.
4. An adiabatic process occurs without loss or gain of heat.
5. An isentropic process (reversible adiabatic process) occurs at a constant entropy.
6. An isenthalpic process occurs at a constant enthalpy. Also known as a throttling process or wire drawing.
7. A steady state process occurs without a change in the internal energy of a system.

The laws of thermodynamics

In thermodynamics, there are four laws of very general validity, and as such they do not depend on the details of the interactions or the systems being studied. Hence, they can be applied to systems about which one knows nothing other than the balance of energy and matter transfer. Examples of this include Einstein's prediction of spontaneous emission around the turn of the 20th century and current research into the thermodynamics of black holes.

The four laws are:
:If two thermodynamic systems are separately in thermal equilibrium with a third, they are also in thermal equilibrium with each other.
:The change in the internal energy of a closed thermodynamic system is equal to the sum of the amount of heat energy supplied to the system and the work done on the system.
:The total entropy of any isolated thermodynamic system tends to increase over time, approaching a maximum value.
:As a system asymptotically approaches absolute zero of temperature all processes virtually cease and the entropy of the system asymptotically approaches a minimum value; also stated as: "the entropy of all systems and of all states of a system is zero at absolute zero" or equivalently "it is impossible to reach the absolute zero of temperature by any finite number of processes".

Thermodynamic potentials

As can be derived from the energy balance equation on a thermodynamic system there exist energetic quantities called thermodynamic potentials, being the quantitative measure of the stored energy in the system. The five most well known potentials are:

 Internal energy Helmholtz free energy Enthalpy Gibbs free energy Grand potential

Potentials are used to measure 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. Internal energy is the internal energy of the system, enthalpy is the internal energy of the system plus the energy related to pressure-volume work, and Helmholtz and Gibbs energy are the energies available in a system to do useful work when the temperature and volume or the pressure and temperature are fixed, respectively.

Quotes & humor

 Thermodynamics is a funny subject. The first time you go through it, you don't understand it at all. The second time you go through it, you think you understand it, except for one or two small points. The third time you go through it, you know you don't understand it, but by that time you are so used to it, it doesn't bother you any more.

References

1. ^ Clark, John, O.E. (2004). The Essential Dictionary of Science. Barnes & Noble Books. ISBN 0-7607-4616-8.
2. ^ Clausius, Ruldolf (1850). On the Motive Power of Heat, and on the Laws which can be deduced from it for the Theory of Heat. Poggendorff's Annalen der Physick, LXXIX (Dover Reprint). ISBN 0-486-59065-8.
3. ^ Van Ness, H.C. (1969). Understanding Thermodynamics. Dover Publications, Inc.. ISBN 0-486-63277-6.
4. ^ Dugdale, J.S. (1998). Entropy and its Physical Meaning. Taylor and Francis. ISBN 0-7484-0569-0.
5. ^ Smith, J.M.; Van Ness, H.C., Abbott, M.M. (2005). Introduction to Chemical Engineering Thermodynamics. McGraw Hill. ISBN 0-07-310445-0.
6. ^ Haynie, Donald, T. (2001). Biological Thermodynamics. Cambridge University Press. ISBN 0-521-79549-4.
7. ^ Partington, J.R. (1989). A Short History of Chemistry. Dover. ISBN 0-486-65977-1.
8. ^ Kelvin, William T. (1849) "An Account of Carnot's Theory of the Motive Power of Heat - with Numerical Results Deduced from Regnault's Experiments on Steam." Transactions of the Edinburg Royal Society, XVI. January 2. Scanned Copy
9. ^ Cengel, Yunus A.; Boles, Michael A. (2005). Thermodynamics - An Engineering Approach. McGraw-Hill. ISBN 0-07-310768-9.
10. ^ Mechanical Theory of Heat, by Rudolf Clausius, 1850-1865
11. ^ Nash, Leonard K. (1974). Elements of Statistical Thermodynamics, 2nd Ed.. Dover Publications, Inc.. ISBN 0-486-44978-5.
12. ^ Gibbs, Willard (1993). The Scientific Papers of J. Willard Gibbs, Volume One: Thermodynamics. Ox Bow Press. ISBN 0-918024-77-3.
13. ^ Lewis, Gilbert N.; Randall, Merle (1923). Thermodynamics and the Free Energy of Chemical Substances. McGraw-Hill Book Co. Inc..

• Cengel, Yunus A.; Boles, Michael A. (2002). Thermodynamics - An Engineering Approach. McGraw Hill. ISBN 0-07-238332-1.
• Kroemer, Herbert; Kittel, Charles (1980). Thermal Physics. W. H. Freeman Company. ISBN 0-7167-1088-9.
• Goldstein, Martin; Inge, F (1993). The Refrigerator and the Universe. Harvard University Press. ISBN 0-674-75325-9.
• Dunning-Davies, Jeremy (1997). Concise Thermodynamics: Principles and Applications. Horwood Publishing. ISBN 1-8985-6315-2.

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In physics, power (symbol: P) is the rate at which work is performed or energy is transmitted, or the amount of energy required or expended for a given unit of time.
Physics is the science of matter[1] and its motion[2][3], as well as space and time[4][5] —the science that deals with concepts such as force, energy, mass, and charge.
trillion fold).]]

Temperature is a physical property of a system that underlies the common notions of hot and cold; something that is hotter generally has the greater temperature. Temperature is one of the principal parameters of thermodynamics.
Pressure (symbol: p) is the force per unit area applied on a surface in a direction perpendicular to that surface.

Gauge pressure is the pressure relative to the local atmospheric or ambient pressure.
The volume of a solid object is the three-dimensional concept of how much space it occupies, often quantified numerically. One-dimensional figures (such as lines) and two-dimensional shapes (such as squares) are assigned zero volume in the three-dimensional space.
system has a technical meaning, namely, it is the portion of the physical universe chosen for analysis. Everything outside the system is known as the environment, which in analysis is ignored except for its effects on the system.
Macroscopic is commonly used to describe physical objects that are measurable and observable by the naked eye. When applied to phenomena and abstract objects, it describes existence in the world as we perceive it.
Statistics is a mathematical science pertaining to the collection, analysis, interpretation or explanation, and presentation of data. It is applicable to a wide variety of academic disciplines, from the physical and social sciences to the humanities.
Editing of this page by unregistered or newly registered users is currently disabled due to vandalism.
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In physics, dynamics is the branch of classical mechanics that is concerned with the effects of forces on the motion of objects. The former distinguishes it from kinematics and the latter distinguishes it from statics.
In thermodynamics, the thermal efficiency () is a dimensionless performance measure of a thermal device such as an internal combustion engine, a boiler, or a furnace, for example. The input, , to the device is heat, or the heat-content of a fuel that is consumed.
steam engine is an external combustion heat engine that makes use of the heat energy that exists in steam, converting it to mechanical work.

Steam engines were used as the prime mover in pumping stations, locomotives, steam ships, traction engines, steam lorries and other
laws of thermodynamics, in principle, describe the specifics for the transport of heat and work in thermodynamic processes. Since their conception, however, these laws have become some of the most important in all of physics and other branches of science connected to thermodynamics.
energy (from the Greek ενεργός, energos, "active, working")[1] is a scalar physical quantity that is a property of objects and systems of objects which is conserved by nature.
In physics, mechanical work is the amount of energy transferred by a force. Like energy, it is a scalar quantity, with SI units of joules. Heat conduction is not considered to be a form of work, since there is no macroscopically measurable force, only microscopic forces occurring
Ice melting - a classic example of entropy increasing[1] described in 1862 by Rudolf Clausius as an increase in the disgregation of the molecules of the body of ice.
In thermodynamics, a thermodynamic system, originally called a working substance, is defined as that part of the universe that is under consideration. A real or imaginary boundary separates the system from the rest of the universe, which is referred to as the environment
In thermodynamics, a thermodynamic system, originally called a working substance, is defined as that part of the universe that is under consideration. A real or imaginary boundary separates the system from the rest of the universe, which is referred to as the environment
equation of state is a relation between state variables.<ref name="Perrot" >Perrot, Pierre (1998). A to Z of Thermodynamics. Oxford University Press. ISBN 0-19-856552-6.
In thermodynamics, the internal energy of a thermodynamic system, or a body with well-defined boundaries, denoted by U, or sometimes E, is the total of the kinetic energy due to the motion of molecules (translational, rotational, vibrational) and
thermodynamic potentials are parameters associated with a thermodynamic system and have the dimensions of energy. They are called "potentials" because in a sense, they describe the amount of potential energy in a thermodynamic system when it is subjected to certain constraints.
A dynamic equilibrium occurs when two reversible processes proceed at the same rate. Many processes (such as some chemical reactions) are reversible and when at dynamic equilibrium the forward reaction will occur at the same rate as the reverse reaction such that there is no
A spontaneous process is a chemical reaction in which a system releases free energy (most often as heat) and moves to a lower, more thermodynamically stable, energy state.[1][2]
Science (from the Latin scientia, 'knowledge'), in the broadest sense, refers to any systematic knowledge or practice.[1] Examples of the broader use included political science and computer science, which are not incorrectly named, but rather named according to
Engineering is the applied science of acquiring and applying knowledge to design, analysis, and/or construction of works for practical purposes. The American Engineers' Council for Professional Development, also known as ECPD,[1] (later ABET [2]
An engine is something that produces an output effect from a given input. The origin of engineering however, came from the design, building and working of (military "engines") because before such devices came to be employed in battles there were very few mechanical devices used.
phase transition or phase change is the transformation of a thermodynamic system from one phase to another. The distinguishing characteristic of a phase transition is an abrupt change in one or more physical properties, in particular the heat capacity, with a small change in