Thermodynamics

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Thermodynamics is a branch of physics that deals with heat, work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these quantities is governed by the four laws of thermodynamics which convey a quantitative description using measurable macroscopic physical quantities, but may be explained in terms of microscopic constituents by statistical mechanics. Thermodynamics applies to a wide variety of topics in science and engineering, especially physical chemistry, biochemistry, chemical engineering and mechanical engineering, but also in other complex fields such as meteorology.

Contents

Historically, thermodynamics developed out of a desire to increase the efficiency of early steam engines, particularly through the work of French physicist Sadi Carnot (1824) who believed that engine efficiency was the key that could help France win the Napoleonic Wars. [1] Scots-Irish physicist Lord Kelvin was the first to formulate a concise definition of thermodynamics in 1854 [2] which stated, "Thermo-dynamics is the subject of the relation of heat to forces acting between contiguous parts of bodies, and the relation of heat to electrical agency." German physicist and mathematician Rudolf Clausius restated Carnot's principle known as the Carnot cycle and gave to the theory of heat a truer and sounder basis. His most important paper, "On the Moving Force of Heat", [3] published in 1850, first stated the second law of thermodynamics. In 1865 he introduced the concept of entropy. In 1870 he introduced the virial theorem, which applied to heat. [4]

The initial application of thermodynamics to mechanical heat engines was quickly extended to the study of chemical compounds and chemical reactions. Chemical thermodynamics studies the nature of the role of entropy in the process of chemical reactions and has provided the bulk of expansion and knowledge of the field. Other formulations of thermodynamics emerged. Statistical thermodynamics, or statistical mechanics, concerns itself with statistical predictions of the collective motion of particles from their microscopic behavior. In 1909, Constantin Carathéodory presented a purely mathematical approach in an axiomatic formulation, a description often referred to as geometrical thermodynamics.

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 transferred between physical systems as heat, as work, and with transfer of matter. [5] 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 system and that can be used to quantify the useful work that can be extracted from the system. [6]

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 for equilibrium 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 of physics and for chemistry, chemical engineering, corrosion engineering, aerospace engineering, mechanical engineering, cell biology, biomedical engineering, materials science, and economics, to name a few. [7] [8]

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 thermodynamicists of the original eight founding schools of thermodynamics. The schools with the most-lasting influence on the modern versions of thermodynamics are the Berlin school, particularly aRudolf Clausius's 1865 textbook The Mechanical Theory of Heat, the Vienna school, with the statistical mechanics of Ludwig Boltzmann, and the Gibbsian school at Yale University of Willard Gibbs' 1876 and his book On the Equilibrium of Heterogeneous Substances which launched chemical thermodynamics. Eight founding schools.png
The thermodynamicists of the original eight founding schools of thermodynamics. The schools with the most-lasting influence on the modern versions of thermodynamics are the Berlin school, particularly aRudolf Clausius's 1865 textbook The Mechanical Theory of Heat, the Vienna school, with the statistical mechanics of Ludwig Boltzmann, and the Gibbsian school at Yale University of Willard Gibbs' 1876 and his book On the Equilibrium of Heterogeneous Substances which launched chemical thermodynamics.

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 Anglo-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. [10] 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 inefficient, 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 increase in steam engine efficiency. [11] 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. [12]

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. [13] 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). The foundations of statistical thermodynamics were set out by physicists such as James Clerk Maxwell, Ludwig Boltzmann, Max Planck, Rudolf Clausius and J. Willard Gibbs.

Clausius, who first stated the basic ideas of the second law in his paper "On the Moving Force of Heat", [3] published in 1850, and is called "one of the founding fathers of thermodynamics", [14] introduced the concept of entropy in 1865.

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 , [15] in which he showed how thermodynamic processes, including chemical reactions, could be graphically analyzed, by studying the energy, entropy, volume, temperature and pressure of the thermodynamic system in such a manner, one can determine if a process would occur spontaneously. [16] Also Pierre Duhem in the 19th century wrote about chemical thermodynamics. [17] During the early 20th century, chemists such as Gilbert N. Lewis, Merle Randall, [18] and E. A. Guggenheim [19] [20] applied the mathematical methods of Gibbs to the analysis of chemical processes.

Etymology

Thermodynamics has an intricate etymology. [21]

By a surface-level analysis, the word consists of two parts that can be traced back to Ancient Greek. Firstly, thermo- ("of heat"; used in words such as thermometer ) can be traced back to the root θέρμη therme, meaning "heat". Secondly, the word dynamics ("science of force [or power]") [22] can be traced back to the root δύναμις dynamis, meaning "power". [23]

In 1849, the adjective thermo-dynamic is used by William Thomson. [24] [25]

In 1854, the noun thermo-dynamics is used by Thomson and William Rankine to represent the science of generalized heat engines. [25] [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, [12] however, Joule never used that term, but used instead the term perfect thermo-dynamic engine in reference to Thomson's 1849 [24] phraseology. [21]

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 of statistical mechanics.

Statistical mechanics

Statistical mechanics, also known as 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.

Chemical thermodynamics

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. The primary objective of chemical thermodynamics is determining the spontaneity of a given transformation. [26]

Equilibrium thermodynamics

Equilibrium thermodynamics is the study of transfers of matter and energy in systems or bodies that, by agencies in their surroundings, can be driven from one state of thermodynamic equilibrium to another. The term 'thermodynamic equilibrium' indicates a state of balance, in which all macroscopic flows are zero; in the case of the simplest systems or bodies, their intensive properties are homogeneous, and their pressures are perpendicular to their boundaries. In an equilibrium state there are no unbalanced potentials, or driving forces, between macroscopically distinct parts of the system. A central aim in equilibrium thermodynamics is: given a system in a well-defined initial equilibrium state, and given its surroundings, and given its constitutive walls, to calculate what will be the final equilibrium state of the system after a specified thermodynamic operation has changed its walls or surroundings.

Non-equilibrium thermodynamics

Non-equilibrium thermodynamics is a branch of thermodynamics that deals with systems that are not in thermodynamic equilibrium. Most systems found in nature are not in thermodynamic equilibrium because they are not in stationary states, and are continuously and discontinuously subject to flux of matter and energy to and from other systems. The thermodynamic study of non-equilibrium systems requires more general concepts than are dealt with by equilibrium thermodynamics. [27] Many natural systems still today remain beyond the scope of currently known macroscopic thermodynamic methods.

Laws of thermodynamics

Annotated color version of the original 1824 Carnot heat engine showing the hot body (boiler), working body (system, steam), and cold body (water), the letters labeled according to the stopping points in Carnot cycle Carnot engine (hot body - working body - cold body).jpg
Annotated color version of the original 1824 Carnot heat engine showing the hot body (boiler), working body (system, steam), and cold body (water), the letters labeled according to the stopping points in Carnot cycle

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

The zeroth law of thermodynamics states: 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 whether 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. [28] 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 separate law of thermodynamics, as its basis in thermodynamical equilibrium was implied in the other laws. The first, second, and third laws had been explicitly stated already, and found common acceptance in the physics community before the importance of the zeroth law for the definition of temperature was realized. As it was impractical to renumber the other laws, it was named the zeroth law.

First law

Opening a bottle of sparkling wine (high-speed photography). The sudden drop of pressure causes a huge drop of temperature. The moisture in the air freezes, creating a smoke of tiny ice crystals. Kurzzeitfotografie sektkorken 06-19-s02 2017-09-03 01 hinnerk-ruemenapf exif.jpg
Opening a bottle of sparkling wine (high-speed photography). The sudden drop of pressure causes a huge drop of temperature. The moisture in the air freezes, creating a smoke of tiny ice crystals.

The first law of thermodynamics states: In a process without transfer of matter, the change in internal energy,, of a thermodynamic system is equal to the energy gained as heat,, less the thermodynamic work,, done by the system on its surroundings. [32] [nb 1]

.

where denotes the change in the internal energy of a closed system (for which heat or work through the system boundary are possible, but matter transfer is not possible), denotes the quantity of energy supplied to the system as heat, and denotes the amount of thermodynamic work done by the system on its surroundings. An equivalent statement is that perpetual motion machines of the first kind are impossible; work done by a system on its surrounding requires that the system's internal energy decrease or be consumed, so that the amount of internal energy lost by that work must be resupplied as heat by an external energy source or as work by an external machine acting on the system (so that is recovered) to make the system work continuously.

For processes that include transfer of matter, a further statement is needed: With due account of the respective fiducial reference states of the systems, when two systems, which may be of different chemical compositions, initially separated only by an impermeable wall, and otherwise isolated, are combined into a new system by the thermodynamic operation of removal of the wall, then

,

whereU0denotes the internal energy of the combined system, andU1andU2denote the internal energies of the respective separated systems.

Adapted for thermodynamics, this law is an expression of the principle of conservation of energy, which states that energy can be transformed (changed from one form to another), but cannot be created or destroyed. [33]

Internal energy is a principal property of the thermodynamic state, while heat and work are modes of energy transfer by which a process may change this state. A change of internal energy of a system may be achieved by any combination of heat added or removed and work performed on or by the system. As a function of state, the internal energy does not depend on the manner, or on the path through intermediate steps, by which the system arrived at its state.

Second law

A traditional version of the second law of thermodynamics states: Heat does not spontaneously flow from a colder body to a hotter body.

The second law refers to a system of matter and radiation, initially with inhomogeneities in temperature, pressure, chemical potential, and other intensive properties, that are due to internal 'constraints', or impermeable rigid walls, within it, or to externally imposed forces. The law observes that, when the system is isolated from the outside world and from those forces, there is a definite thermodynamic quantity, its entropy, that increases as the constraints are removed, eventually reaching a maximum value at thermodynamic equilibrium, when the inhomogeneities practically vanish. For systems that are initially far from thermodynamic equilibrium, though several have been proposed, there is known no general physical principle that determines the rates of approach to thermodynamic equilibrium, and thermodynamics does not deal with such rates. The many versions of the second law all express the general irreversibility of the transitions involved in systems approaching thermodynamic equilibrium.

In macroscopic thermodynamics, the second law is a basic observation applicable to any actual thermodynamic process; in statistical thermodynamics, the second law is postulated to be a consequence of molecular chaos.

Third law

The third law of thermodynamics states: As the temperature of a system approaches absolute zero, all processes cease and the entropy of the system approaches a minimum value.

This 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 include "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 achieve, is −273.15 °C (degrees Celsius), or −459.67 °F (degrees Fahrenheit), or 0 K (kelvin), or 0° R (degrees Rankine).

System models

A diagram of a generic thermodynamic system System boundary.svg
A diagram of a generic thermodynamic system

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 or notional, but serve to confine the system to a finite volume. Segments of the boundary are often described as walls; they have respective defined 'permeabilities'. Transfers of energy as work, or as heat, or of matter, between the system and the surroundings, take place through the walls, according to their respective permeabilities.

Matter or energy that pass across the boundary so as to effect a change in the internal energy of the system need to be accounted for in the energy balance equation. The volume contained by the walls 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. The system could also be just one nuclide (i.e. a system of quarks) as hypothesized in quantum thermodynamics. When a looser viewpoint is adopted, and the requirement of thermodynamic equilibrium is dropped, the system can be the body of a tropical cyclone, such as Kerry Emanuel theorized in 1986 in the field of atmospheric thermodynamics, or the event horizon of a black hole.

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:

Interactions of thermodynamic systems
Type of system Mass flow Work Heat
Open Green check.svgYGreen check.svgYGreen check.svgY
Closed Red x.svgNGreen check.svgYGreen check.svgY
Thermally isolated Red x.svgNGreen check.svgYRed x.svgN
Mechanically isolated Red x.svgNRed x.svgNGreen check.svgY
Isolated Red x.svgNRed x.svgNRed x.svgN

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 a state 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.

States and processes

When a system is at equilibrium under a given set of conditions, it is said to be in a definite thermodynamic state. The state of the system can be described by a number of state quantities that do not depend on the process by which the system arrived at its state. They are called intensive variables or extensive variables according to how they change when the size of the system changes. 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.

A thermodynamic process may 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 of a conjugate 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. 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 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. The ocean can act as temperature reservoir when used to cool power plants.

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 equaling 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.

The five most well known potentials are:

NameSymbolFormulaNatural variables
Internal energy
Helmholtz free energy
Enthalpy
Gibbs free energy
Landau potential, or
grand potential
,

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 through Legendre transformation.

Axiomatic thermodynamics

Axiomatic thermodynamics is a mathematical discipline that aims to describe thermodynamics in terms of rigorous axioms, for example by finding a mathematically rigorous way to express the familiar laws of thermodynamics.

The first attempt at an axiomatic theory of thermodynamics was Constantin Carathéodory's 1909 work Investigations on the Foundations of Thermodynamics, which made use of Pfaffian systems and the concept of adiabatic accessibility, a notion that was introduced by Carathéodory himself. [34] [35] In this formulation, thermodynamic concepts such as heat, entropy, and temperature are derived from quantities that are more directly measurable. [36] Theories that came after, differed in the sense that they made assumptions regarding thermodynamic processes with arbitrary initial and final states, as opposed to considering only neighboring states.

Applied fields

See also

Lists and timelines

Notes

  1. The sign convention (Q is heat supplied to the system as, W is work done by the system) is that of Rudolf Clausius. The opposite sign convention is customary in chemical thermodynamics.

Related Research Articles

Chemical thermodynamics is the study of the interrelation of heat and work with chemical reactions or with physical changes of state within the confines of the laws of thermodynamics. Chemical thermodynamics involves not only laboratory measurements of various thermodynamic properties, but also the application of mathematical methods to the study of chemical questions and the spontaneity of processes.

<span class="mw-page-title-main">Entropy</span> Property of a thermodynamic system

Entropy is a scientific concept that is most commonly associated with a state of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics, where it was first recognized, to the microscopic description of nature in statistical physics, and to the principles of information theory. It has found far-ranging applications in chemistry and physics, in biological systems and their relation to life, in cosmology, economics, sociology, weather science, climate change, and information systems including the transmission of information in telecommunication.

<span class="mw-page-title-main">Thermodynamic free energy</span> State function whose change relates to the systems maximal work output

In thermodynamics, the thermodynamic free energy is one of the state functions of a thermodynamic system. The change in the free energy is the maximum amount of work that the system can perform in a process at constant temperature, and its sign indicates whether the process is thermodynamically favorable or forbidden. Since free energy usually contains potential energy, it is not absolute but depends on the choice of a zero point. Therefore, only relative free energy values, or changes in free energy, are physically meaningful.

<span class="mw-page-title-main">Second law of thermodynamics</span> Physical law for entropy and heat

The second law of thermodynamics is a physical law based on universal empirical observation concerning heat and energy interconversions. A simple statement of the law is that heat always flows spontaneously from hotter to colder regions of matter. Another statement is: "Not all heat can be converted into work in a cyclic process."

<span class="mw-page-title-main">First law of thermodynamics</span> Law of thermodynamics establishing the conservation of energy

The first law of thermodynamics is a formulation of the law of conservation of energy in the context of thermodynamic processes. The law distinguishes two principal forms of energy transfer, heat and thermodynamic work, that modify a thermodynamic system containing a constant amount of matter. The law also defines the internal energy of a system, an extensive property for taking account of the balance of heat and work in the system. Energy cannot be created or destroyed, but it can be transformed from one form to another. In an isolated system the sum of all forms of energy is constant.

<span class="mw-page-title-main">Reversible process (thermodynamics)</span> Thermodynamic process whose direction can be reversed to return the system to its original state

In thermodynamics, a reversible process is a process, involving a system and its surroundings, whose direction can be reversed by infinitesimal changes in some properties of the surroundings, such as pressure or temperature.

<span class="mw-page-title-main">Thermodynamic system</span> Body of matter in a state of internal equilibrium

A thermodynamic system is a body of matter and/or radiation separate from its surroundings that can be studied using the laws of thermodynamics.

<span class="mw-page-title-main">Non-equilibrium thermodynamics</span> Branch of thermodynamics

Non-equilibrium thermodynamics is a branch of thermodynamics that deals with physical systems that are not in thermodynamic equilibrium but can be described in terms of macroscopic quantities that represent an extrapolation of the variables used to specify the system in thermodynamic equilibrium. Non-equilibrium thermodynamics is concerned with transport processes and with the rates of chemical reactions.

<span class="mw-page-title-main">Laws of thermodynamics</span> Observational basis of thermodynamics

The laws of thermodynamics are a set of scientific laws which define a group of physical quantities, such as temperature, energy, and entropy, that characterize thermodynamic systems in thermodynamic equilibrium. The laws also use various parameters for thermodynamic processes, such as thermodynamic work and heat, and establish relationships between them. They state empirical facts that form a basis of precluding the possibility of certain phenomena, such as perpetual motion. In addition to their use in thermodynamics, they are important fundamental laws of physics in general and are applicable in other natural sciences.

Exergy, often referred to as "available energy" or "useful work potential", is a fundamental concept in the field of thermodynamics and engineering. It plays a crucial role in understanding and quantifying the quality of energy within a system and its potential to perform useful work. Exergy analysis has widespread applications in various fields, including energy engineering, environmental science, and industrial processes.

<span class="mw-page-title-main">Thermodynamic equations</span> Equations in thermodynamics

Thermodynamics is expressed by a mathematical framework of thermodynamic equations which relate various thermodynamic quantities and physical properties measured in a laboratory or production process. Thermodynamics is based on a fundamental set of postulates, that became the laws of thermodynamics.

<span class="mw-page-title-main">Equilibrium thermodynamics</span>

Equilibrium Thermodynamics is the systematic study of transformations of matter and energy in systems in terms of a concept called thermodynamic equilibrium. The word equilibrium implies a state of balance. Equilibrium thermodynamics, in origins, derives from analysis of the Carnot cycle. Here, typically a system, as cylinder of gas, initially in its own state of internal thermodynamic equilibrium, is set out of balance via heat input from a combustion reaction. Then, through a series of steps, as the system settles into its final equilibrium state, work is extracted.

<span class="mw-page-title-main">Work (thermodynamics)</span> Type of energy transfer

Thermodynamic work is one of the principal processes by which a thermodynamic system can interact with its surroundings and exchange energy. This exchange results in externally measurable macroscopic forces on the system's surroundings, which can cause mechanical work, to lift a weight, for example, or cause changes in electromagnetic, or gravitational variables. The surroundings also can perform work on a thermodynamic system, which is measured by an opposite sign convention.

The concept of entropy developed in response to the observation that a certain amount of functional energy released from combustion reactions is always lost to dissipation or friction and is thus not transformed into useful work. Early heat-powered engines such as Thomas Savery's (1698), the Newcomen engine (1712) and the Cugnot steam tricycle (1769) were inefficient, converting less than two percent of the input energy into useful work output; a great deal of useful energy was dissipated or lost. Over the next two centuries, physicists investigated this puzzle of lost energy; the result was the concept of entropy.

In classical thermodynamics, entropy is a property of a thermodynamic system that expresses the direction or outcome of spontaneous changes in the system. The term was introduced by Rudolf Clausius in the mid-19th century to explain the relationship of the internal energy that is available or unavailable for transformations in form of heat and work. Entropy predicts that certain processes are irreversible or impossible, despite not violating the conservation of energy. The definition of entropy is central to the establishment of the second law of thermodynamics, which states that the entropy of isolated systems cannot decrease with time, as they always tend to arrive at a state of thermodynamic equilibrium, where the entropy is highest. Entropy is therefore also considered to be a measure of disorder in the system.

The concept entropy was first developed by German physicist Rudolf Clausius in the mid-nineteenth century as a thermodynamic property that predicts that certain spontaneous processes are irreversible or impossible. In statistical mechanics, entropy is formulated as a statistical property using probability theory. The statistical entropy perspective was introduced in 1870 by Austrian physicist Ludwig Boltzmann, who established a new field of physics that provided the descriptive linkage between the macroscopic observation of nature and the microscopic view based on the rigorous treatment of large ensembles of microscopic states that constitute thermodynamic systems.

Atmospheric thermodynamics is the study of heat-to-work transformations that take place in the Earth's atmosphere and manifest as weather or climate. Atmospheric thermodynamics use the laws of classical thermodynamics, to describe and explain such phenomena as the properties of moist air, the formation of clouds, atmospheric convection, boundary layer meteorology, and vertical instabilities in the atmosphere. Atmospheric thermodynamic diagrams are used as tools in the forecasting of storm development. Atmospheric thermodynamics forms a basis for cloud microphysics and convection parameterizations used in numerical weather models and is used in many climate considerations, including convective-equilibrium climate models.

<span class="mw-page-title-main">Introduction to entropy</span> Non-technical introduction to entropy

In thermodynamics, entropy is a numerical quantity that shows that many physical processes can go in only one direction in time. For example, cream and coffee can be mixed together, but cannot be "unmixed"; a piece of wood can be burned, but cannot be "unburned". The word 'entropy' has entered popular usage to refer a lack of order or predictability, or of a gradual decline into disorder. A more physical interpretation of thermodynamic entropy refers to spread of energy or matter, or to extent and diversity of microscopic motion.

<span class="mw-page-title-main">Heat</span> Type of energy transfer

In thermodynamics, heat is the thermal energy transferred between systems due to a temperature difference. In colloquial use, heat sometimes refers to thermal energy itself. Thermal energy is the kinetic energy of vibrating and colliding atoms in a substance.

<span class="mw-page-title-main">Temperature</span> Physical quantity of hot and cold

Temperature is a physical quantity that quantitatively expresses the attribute of hotness or coldness. Temperature is measured with a thermometer. It reflects the average kinetic energy of the vibrating and colliding atoms making up a substance.

References

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  11. The Newcomen engine was improved from 1711 until Watt's work, making the efficiency comparison subject to qualification, but the increase from the 1865 version was on the order of 100%.
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  35. Frankel, Theodore (2004). The Geometry of Physics: An Introduction (second ed.). Cambridge University Press. ISBN   9780521539272.
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Further reading

The following titles are more technical: