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In science, a process that is not reversible is called irreversible. This concept arises frequently in
thermodynamics 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 ...
. All complex natural processes are irreversible, although a
phase transition In chemistry, thermodynamics, and other related fields, a phase transition (or phase change) is the physical process of transition between one state of a medium and another. Commonly the term is used to refer to changes among the basic states ...
at the coexistence temperature (e.g. melting of ice cubes in water) is well approximated as reversible. In thermodynamics, a change in the
thermodynamic state In thermodynamics, a thermodynamic state of a system is its condition at a specific time; that is, fully identified by values of a suitable set of parameters known as state variables, state parameters or thermodynamic variables. Once such a set ...
of a system and all of its surroundings cannot be precisely restored to its initial state by
infinitesimal In mathematics, an infinitesimal number is a quantity that is closer to zero than any standard real number, but that is not zero. The word ''infinitesimal'' comes from a 17th-century Modern Latin coinage ''infinitesimus'', which originally re ...
changes in some property of the system without expenditure of energy. A system that undergoes an irreversible process may still be capable of returning to its initial state. Because entropy is a
state function In the thermodynamics of equilibrium, a state function, function of state, or point function for a thermodynamic system is a mathematical function relating several state variables or state quantities (that describe equilibrium states of a system ...
, the change in entropy of the system is the same whether the process is reversible or irreversible. However, the impossibility occurs in restoring the
environment Environment most often refers to: __NOTOC__ * Natural environment, all living and non-living things occurring naturally * Biophysical environment, the physical and biological factors along with their chemical interactions that affect an organism or ...
to its own initial conditions. An irreversible process increases the total
entropy Entropy is a scientific concept, as well as a measurable physical property, 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 thermodyna ...
of the system and its surroundings. The
second law of thermodynamics The second law of thermodynamics is a physical law based on universal experience concerning heat and energy interconversions. One simple statement of the law is that heat always moves from hotter objects to colder objects (or "downhill"), unle ...
can be used to determine whether a hypothetical process is reversible or not. Intuitively, a process is reversible if there is no dissipation. For example,
Joule expansion The Joule expansion (also called free expansion) is an irreversible process in thermodynamics in which a volume of gas is kept in one side of a thermally isolated container (via a small partition), with the other side of the container being evacu ...
is irreversible because initially the system is not uniform. Initially, there is part of the system with gas in it, and part of the system with no gas. For dissipation to occur, there needs to be such a non uniformity. This is just the same as if in a system one section of the gas was hot, and the other cold. Then dissipation would occur; the temperature distribution would become uniform with no work being done, and this would be irreversible because you couldn't add or remove heat or change the volume to return the system to its initial state. Thus, if the system is always uniform, then the process is reversible, meaning that you can return the system to its original state by either adding or removing heat, doing work on the system, or letting the system do work. As another example, to approximate the expansion in an internal combustion engine as reversible, we would be assuming that the temperature and pressure uniformly change throughout the volume after the spark. Obviously, this is not true and there is a flame front and sometimes even
engine knocking In spark ignition internal combustion engines, knocking (also knock, detonation, spark knock, pinging or pinking) occurs when combustion of some of the air/fuel mixture in the cylinder does not result from propagation of the flame front ignit ...
. One of the reasons that Diesel engines are able to attain higher efficiency is that the combustion is much more uniform, so less energy is lost to dissipation and the process is closer to reversible. The phenomenon of irreversibility results from the fact that if a
thermodynamic system A thermodynamic system is a body of matter and/or radiation, confined in space by walls, with defined permeabilities, which separate it from its surroundings. The surroundings may include other thermodynamic systems, or physical systems that are ...
, which is any system of sufficient complexity, of interacting molecules is brought from one thermodynamic state to another, the configuration or arrangement of the atoms and molecules in the system will change in a way that is not easily predictable. Some "transformation energy" will be used as the molecules of the "working body" do work on each other when they change from one state to another. During this transformation, there will be some heat energy loss or
dissipation In thermodynamics, dissipation is the result of an irreversible process that takes place in homogeneous thermodynamic systems. In a dissipative process, energy ( internal, bulk flow kinetic, or system potential) transforms from an initial form to ...
due to intermolecular friction and collisions. This energy will not be recoverable if the process is reversed. Many
biological Biology is the scientific study of life. It is a natural science with a broad scope but has several unifying themes that tie it together as a single, coherent field. For instance, all organisms are made up of cells that process hereditary in ...
processes that were once thought to be reversible have been found to actually be a pairing of two irreversible processes. Whereas a single enzyme was once believed to catalyze both the forward and reverse chemical changes, research has found that two separate enzymes of similar structure are typically needed to perform what results in a pair of thermodynamically irreversible processes.


Absolute versus statistical reversibility

Thermodynamics defines the statistical behaviour of large numbers of entities, whose exact behavior is given by more specific laws. While the fundamental theoretical laws of physics are all time-reversible, experimentally the probability of real reversibility is low and the former state of system and surroundings is recovered only to certain extent (see:
uncertainty principle In quantum mechanics, the uncertainty principle (also known as Heisenberg's uncertainty principle) is any of a variety of mathematical inequalities asserting a fundamental limit to the accuracy with which the values for certain pairs of physic ...
). The reversibility of thermodynamics must be statistical in nature; that is, it must be merely highly unlikely, but not impossible, that a system will lower in entropy. In other words, time reversibility is fulfilled if the process happens the same way if time were to flow in reverse or the order of states in the process is reversed (the last state becomes the first and vice versa).


History

The German physicist
Rudolf Clausius Rudolf Julius Emanuel Clausius (; 2 January 1822 – 24 August 1888) was a German physicist and mathematician and is considered one of the central founding fathers of the science of thermodynamics. By his restatement of Sadi Carnot's princip ...
, in the 1850s, was the first to mathematically quantify the discovery of irreversibility in nature through his introduction of the concept of
entropy Entropy is a scientific concept, as well as a measurable physical property, 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 thermodyna ...
. In his 1854 memoir "On a Modified Form of the Second Fundamental Theorem in the Mechanical Theory of Heat," Clausius states: Simply, Clausius states that it is impossible for a system to transfer heat from a cooler body to a hotter body. For example, a cup of hot coffee placed in an area of room temperature will transfer heat to its surroundings and thereby cool down with the temperature of the room slightly increasing (to ). However, that same initial cup of coffee will never absorb heat from its surroundings, causing it to grow even hotter, with the temperature of the room decreasing (to ). Therefore, the process of the coffee cooling down is irreversible unless extra energy is added to the system. However, a paradox arose when attempting to reconcile microanalysis of a system with observations of its macrostate. Many processes are mathematically reversible in their microstate when analyzed using classical Newtonian mechanics. This paradox clearly taints microscopic explanations of macroscopic tendency towards equilibrium, such as
James Clerk Maxwell James Clerk Maxwell (13 June 1831 – 5 November 1879) was a Scottish mathematician and scientist responsible for the classical theory of electromagnetic radiation, which was the first theory to describe electricity, magnetism and ligh ...
's 1860 argument that molecular collisions entail an equalization of temperatures of mixed gases. From 1872 to 1875,
Ludwig Boltzmann Ludwig Eduard Boltzmann (; 20 February 1844 – 5 September 1906) was an Austrian physicist and philosopher. His greatest achievements were the development of statistical mechanics, and the statistical explanation of the second law of ther ...
reinforced the statistical explanation of this paradox in the form of
Boltzmann's entropy formula In statistical mechanics, Boltzmann's equation (also known as the Boltzmann–Planck equation) is a probability equation relating the entropy S, also written as S_\mathrm, of an ideal gas to the multiplicity (commonly denoted as \Omega or W), the ...
, stating that an increase of the number of possible microstates a system might be in, will increase the entropy of the system, making it less likely that the system will return to an earlier state. His formulas quantified the analysis done by
William Thomson, 1st Baron Kelvin William Thomson, 1st Baron Kelvin, (26 June 182417 December 1907) was a British mathematician, Mathematical physics, mathematical physicist and engineer born in Belfast. Professor of Natural Philosophy (Glasgow), Professor of Natural Philoso ...
, who had argued that: Another explanation of irreversible systems was presented by French mathematician
Henri Poincaré Jules Henri Poincaré ( S: stress final syllable ; 29 April 1854 – 17 July 1912) was a French mathematician, theoretical physicist, engineer, and philosopher of science. He is often described as a polymath, and in mathematics as "Th ...
. In 1890, he published his first explanation of nonlinear dynamics, also called
chaos theory Chaos theory is an interdisciplinary area of scientific study and branch of mathematics focused on underlying patterns and deterministic laws of dynamical systems that are highly sensitive to initial conditions, and were once thought to hav ...
. Applying chaos theory to the
second law of thermodynamics The second law of thermodynamics is a physical law based on universal experience concerning heat and energy interconversions. One simple statement of the law is that heat always moves from hotter objects to colder objects (or "downhill"), unle ...
, the paradox of irreversibility can be explained in the errors associated with scaling from microstates to macrostates and the degrees of freedom used when making experimental observations. Sensitivity to initial conditions relating to the system and its environment at the microstate compounds into an exhibition of irreversible characteristics within the observable, physical realm.


Examples of irreversible processes

In the physical realm, many irreversible processes are present to which the inability to achieve 100% efficiency in energy transfer can be attributed. The following is a list of spontaneous events which contribute to the irreversibility of processes. *
Ageing Ageing ( BE) or aging ( AE) is the process of becoming older. The term refers mainly to humans, many other animals, and fungi, whereas for example, bacteria, perennial plants and some simple animals are potentially biologically immortal. ...
(this claim is disputed, as aging has been demonstrated to be reversed in mice.
NAD+ Nicotinamide adenine dinucleotide (NAD) is a coenzyme central to metabolism. Found in all living cells, NAD is called a dinucleotide because it consists of two nucleotides joined through their phosphate groups. One nucleotide contains an ade ...
and
telomerase Telomerase, also called terminal transferase, is a ribonucleoprotein that adds a species-dependent telomere repeat sequence to the 3' end of telomeres. A telomere is a region of repetitive sequences at each end of the chromosomes of most euk ...
have also been demonstrated to reverse ageing.) *
Death Death is the irreversible cessation of all biological functions that sustain an organism. For organisms with a brain, death can also be defined as the irreversible cessation of functioning of the whole brain, including brainstem, and brain ...
*
Time Time is the continued sequence of existence and event (philosophy), events that occurs in an apparently irreversible process, irreversible succession from the past, through the present, into the future. It is a component quantity of various me ...
*
Heat transfer Heat transfer is a discipline of thermal engineering that concerns the generation, use, conversion, and exchange of thermal energy ( heat) between physical systems. Heat transfer is classified into various mechanisms, such as thermal conducti ...
through a finite temperature difference *
Friction Friction is the force resisting the relative motion of solid surfaces, fluid layers, and material elements sliding against each other. There are several types of friction: *Dry friction is a force that opposes the relative lateral motion of ...
*
Plastic deformation In engineering, deformation refers to the change in size or shape of an object. ''Displacements'' are the ''absolute'' change in position of a point on the object. Deflection is the relative change in external displacements on an object. Strain ...
* Flow of electric current through a resistance * Magnetization or polarization with a hysteresis * Unrestrained expansion of fluids * Spontaneous chemical reactions * Spontaneous mixing of matter of varying composition/states A
Joule expansion The Joule expansion (also called free expansion) is an irreversible process in thermodynamics in which a volume of gas is kept in one side of a thermally isolated container (via a small partition), with the other side of the container being evacu ...
is an example of classical thermodynamics, as it is easy to work out the resulting increase in entropy. It occurs where a volume of gas is kept in one side of a thermally isolated container (via a small partition), with the other side of the container being evacuated; the partition between the two parts of the container is then opened, and the gas fills the whole container. The internal energy of the gas remains the same, while the volume increases. The original state cannot be recovered by simply compressing the gas to its original volume, since the internal energy will be increased by this compression. The original state can only be recovered by then cooling the re-compressed system, and thereby irreversibly heating the environment. The diagram to the right applies only if the first expansion is "free" (Joule expansion), i.e. there can be no atmospheric pressure outside the cylinder and no weight lifted.


Complex systems

The difference between reversible and irreversible events has particular explanatory value in
complex system A complex system is a system composed of many components which may interact with each other. Examples of complex systems are Earth's global climate, organisms, the human brain, infrastructure such as power grid, transportation or communication sy ...
s (such as living organisms, or
ecosystems An ecosystem (or ecological system) consists of all the organisms and the physical environment with which they interact. These biotic and abiotic components are linked together through nutrient cycles and energy flows. Energy enters the syst ...
). According to the biologists
Humberto Maturana Humberto Maturana Romesín (September 14, 1928 – May 6, 2021) was a Chilean biologist and philosopher. Many consider him a member of a group of second-order cybernetics theoreticians such as Heinz von Foerster, Gordon Pask, Herbert Brün a ...
and
Francisco Varela Francisco Javier Varela García (September 7, 1946 – May 28, 2001) was a Chilean biologist, philosopher, cybernetician, and neuroscientist who, together with his mentor Humberto Maturana, is best known for introducing the concept of autopoiesi ...
, living organisms are characterized by
autopoiesis The term autopoiesis () refers to a system capable of producing and maintaining itself by creating its own parts. The term was introduced in the 1972 publication '' Autopoiesis and Cognition: The Realization of the Living'' by Chilean biologists ...
, which enables their continued existence. More primitive forms of self-organizing systems have been described by the physicist and chemist Ilya Prigogine. In the context of complex systems, events which lead to the end of certain self-organising processes, like
death Death is the irreversible cessation of all biological functions that sustain an organism. For organisms with a brain, death can also be defined as the irreversible cessation of functioning of the whole brain, including brainstem, and brain ...
, extinction of a species or the collapse of a meteorological system can be considered as irreversible. Even if a clone with the same organizational principle (e.g. identical DNA-structure) could be developed, this would not mean that the former distinct system comes back into being. Events to which the self-organizing capacities of organisms, species or other complex systems can adapt, like minor injuries or changes in the physical environment are reversible. However, adaptation depends on import of
negentropy In information theory and statistics, negentropy is used as a measure of distance to normality. The concept and phrase "negative entropy" was introduced by Erwin Schrödinger in his 1944 popular-science book ''What is Life?'' Later, Léon Brillo ...
into the organism, thereby increasing irreversible processes in its environment. Ecological principles, like those of
sustainability Specific definitions of sustainability are difficult to agree on and have varied in the literature and over time. The concept of sustainability can be used to guide decisions at the global, national, and individual levels (e.g. sustainable livi ...
and the precautionary principle can be defined with reference to the concept of reversibility. Lucia U., 2010, Maximum entropy generation and κ−exponential model, ''Physica A'' 389, pp. 4558-4563


See also

*
Entropy production Entropy production (or generation) is the amount of entropy which is produced in any irreversible processes such as heat and mass transfer processes including motion of bodies, heat exchange, fluid flow, substances expanding or mixing, anelastic ...
*
Entropy (arrow of time) Entropy is one of the few quantities in the physical sciences that require a particular direction for time, sometimes called an arrow of time. As one goes "forward" in time, the second law of thermodynamics says, the entropy of an isolated system ca ...
*
Exergy In thermodynamics, the exergy of a system is the maximum useful work possible during a process that brings the system into equilibrium with a heat reservoir, reaching maximum entropy. When the surroundings are the reservoir, exergy is the pot ...
*
Reversible process (thermodynamics) 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. Throughout an ...
* One way function *
Non-equilibrium 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 (non-equilibrium state variables) that represent an ext ...
*
Symmetry breaking In physics, symmetry breaking is a phenomenon in which (infinitesimally) small fluctuations acting on a system crossing a critical point decide the system's fate, by determining which branch of a bifurcation is taken. To an outside observe ...


References

{{DEFAULTSORT:Irreversible Process (Thermodynamics) Thermodynamics