Thermodynamic free energy

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The thermodynamic free energy is a concept useful in the thermodynamics of chemical or thermal processes in engineering and science. The change in the free energy is the maximum amount of work that a thermodynamic 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.

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The free energy is a thermodynamic state function, like the internal energy, enthalpy, and entropy.

The free energy is the portion of any first-law energy that is available to perform thermodynamic work at constant temperature, i.e., work mediated by thermal energy. Free energy is subject to irreversible loss in the course of such work. [1] Since first-law energy is always conserved, it is evident that free energy is an expendable, second-law kind of energy. Several free energy functions may be formulated based on system criteria. Free energy functions are Legendre transforms of the internal energy.

The Gibbs free energy is given by G = HTS, where H is the enthalpy, T is the absolute temperature, and S is the entropy. H = U + pV, where U is the internal energy, p is the pressure, and V is the volume. G is the most useful for processes involving a system at constant pressure p and temperature T, because, in addition to subsuming any entropy change due merely to heat, a change in G also excludes the pdV work needed to "make space for additional molecules" produced by various processes. Gibbs free energy change therefore equals work not associated with system expansion or compression, at constant temperature and pressure. (Hence its utility to solution-phase chemists, including biochemists.)

The, historically earlier, Helmholtz free energy is defined in contrast as A = UTS. Its change is equal to the amount of reversible work done on, or obtainable from, a system at constant T. Thus its appellation "work content", and the designation A from Arbeit, the German word for work. Since it makes no reference to any quantities involved in work (such as p and V), the Helmholtz function is completely general: its decrease is the maximum amount of work which can be done by a system at constant temperature, and it can increase at most by the amount of work done on a system isothermally. The Helmholtz free energy has a special theoretical importance since it is proportional to the logarithm of the partition function for the canonical ensemble in statistical mechanics. (Hence its utility to physicists; and to gas-phase chemists and engineers, who do not want to ignore pdV work.)

Historically, the term 'free energy' has been used for either quantity. In physics, free energy most often refers to the Helmholtz free energy, denoted by A (or F), while in chemistry, free energy most often refers to the Gibbs free energy. The values of the two free energies are usually quite similar and the intended free energy function is often implicit in manuscripts and presentations.

Meaning of "free"

The basic definition of "energy" is a measure of a body's (in thermodynamics, the system's) ability to cause change. For example, when a person pushes a heavy box a few metres forward, that person exerts mechanical energy, also known as work, on the box over a distance of a few meters forward. The mathematical definition of this form of energy is the product of the force exerted on the object and the distance by which the box moved (Work = Force × Distance). Because the person changed the stationary position of the box, that person exerted energy on that box. The work exerted can also be called "useful energy", because energy was converted from one form into the intended purpose, i.e. mechanical utilisation. For the case of the person pushing the box, the energy in the form of internal (or potential) energy obtained through metabolism was converted into work in order to push the box. This energy conversion, however, was not straightforward: while some internal energy went into pushing the box, some was diverted away (lost) in the form of heat (transferred thermal energy). For a reversible process, heat is the product of the absolute temperature and the change in entropy of a body (entropy is a measure of disorder in a system). The difference between the change in internal energy, which is , and the energy lost in the form of heat is what is called the "useful energy" of the body, or the work of the body performed on an object. In thermodynamics, this is what is known as "free energy". In other words, free energy is a measure of work (useful energy) a system can perform at constant temperature. Mathematically, free energy is expressed as:

free energy

This expression has commonly been interpreted to mean that work is extracted from the internal energy while represents energy not available to perform work. However, this is incorrect. For instance, in an isothermal expansion of an ideal gas, the internal energy change is and the expansion work is derived exclusively from the term supposedly not available to perform work. But it is noteworthy that the derivative form of the free energy: (for Helmholtz free energy) does indeed indicate that a spontaneous change in a non-reactive system's free energy (NOT the internal energy) comprises the available energy to do work (compression in this case) and the unavailable energy . [2] [3] [4] Similar expression can be written for the Gibbs free energy change. [5] [3] [4]

In the 18th and 19th centuries, the theory of heat, i.e., that heat is a form of energy having relation to vibratory motion, was beginning to supplant both the caloric theory, i.e., that heat is a fluid, and the four element theory, in which heat was the lightest of the four elements. In a similar manner, during these years, heat was beginning to be distinguished into different classification categories, such as “free heat”, “combined heat”, “radiant heat”, specific heat, heat capacity, “absolute heat”, “latent caloric”, “free” or “perceptible” caloric (calorique sensible), among others.

In 1780, for example, Laplace and Lavoisier stated: “In general, one can change the first hypothesis into the second by changing the words ‘free heat, combined heat, and heat released’ into ‘vis viva, loss of vis viva, and increase of vis viva.’” In this manner, the total mass of caloric in a body, called absolute heat, was regarded as a mixture of two components; the free or perceptible caloric could affect a thermometer, whereas the other component, the latent caloric, could not. [6] The use of the words “latent heat” implied a similarity to latent heat in the more usual sense; it was regarded as chemically bound to the molecules of the body. In the adiabatic compression of a gas, the absolute heat remained constant but the observed rise in temperature implied that some latent caloric had become “free” or perceptible.

During the early 19th century, the concept of perceptible or free caloric began to be referred to as “free heat” or heat set free. In 1824, for example, the French physicist Sadi Carnot, in his famous “Reflections on the Motive Power of Fire”, speaks of quantities of heat ‘absorbed or set free’ in different transformations. In 1882, the German physicist and physiologist Hermann von Helmholtz coined the phrase ‘free energy’ for the expression ETS, in which the change in A (or G) determines the amount of energy ‘free’ for work under the given conditions, specifically constant temperature. [7] :235

Thus, in traditional use, the term “free” was attached to Gibbs free energy for systems at constant pressure and temperature, or to Helmholtz free energy for systems at constant temperature, to mean ‘available in the form of useful work.’ [8] With reference to the Gibbs free energy, we need to add the qualification that it is the energy free for non-volume work and compositional changes. [9] :77–79

An increasing number of books and journal articles do not include the attachment “free”, referring to G as simply Gibbs energy (and likewise for the Helmholtz energy). This is the result of a 1988 IUPAC meeting to set unified terminologies for the international scientific community, in which the adjective ‘free’ was supposedly banished. [10] [11] [12] This standard, however, has not yet been universally adopted, and many published articles and books still include the descriptive ‘free’.[ citation needed ]

Application

Just like the general concept of energy, free energy has a few definitions suitable for different conditions. In physics, chemistry, and biology, these conditions are thermodynamic parameters (temperature , volume , pressure , etc.). Scientists have come up with several ways to define free energy. The mathematical expression of Helmholtz free energy is:

This definition of free energy is useful for gas-phase reactions or in physics when modeling the behavior of isolated systems kept at a constant volume. For example, if a researcher wanted to perform a combustion reaction in a bomb calorimeter, the volume is kept constant throughout the course of a reaction. Therefore, the heat of the reaction is a direct measure of the free energy change, . In solution chemistry, on the other hand, most chemical reactions are kept at constant pressure. Under this condition, the heat of the reaction is equal to the enthalpy change of the system. Under constant pressure and temperature, the free energy in a reaction is known as Gibbs free energy .

These functions have a minimum in chemical equilibrium, as long as certain variables (, and or ) are held constant. In addition, they also have theoretical importance in deriving Maxwell relations. Work other than pdV may be added, e.g., for electrochemical cells, or fdx work in elastic materials and in muscle contraction. Other forms of work which must sometimes be considered are stress-strain, magnetic, as in adiabatic demagnetization used in the approach to absolute zero, and work due to electric polarization. These are described by tensors.

In most cases of interest there are internal degrees of freedom and processes, such as chemical reactions and phase transitions, which create entropy. Even for homogeneous "bulk" materials, the free energy functions depend on the (often suppressed) composition, as do all proper thermodynamic potentials (extensive functions), including the internal energy.

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

is the number of molecules (alternatively, moles) of type in the system. If these quantities do not appear, it is impossible to describe compositional changes. The differentials for processes at uniform pressure and temperature are (assuming only work):

where μi is the chemical potential for the ith component in the system. The second relation is especially useful at constant and , conditions which are easy to achieve experimentally, and which approximately characterize living creatures. Under these conditions, it simplifies to

Any decrease in the Gibbs function of a system is the upper limit for any isothermal, isobaric work that can be captured in the surroundings, or it may simply be dissipated, appearing as times a corresponding increase in the entropy of the system and/or its surrounding.

An example is surface free energy, the amount of increase of free energy when the area of surface increases by every unit area.

The path integral Monte Carlo method is a numerical approach for determining the values of free energies, based on quantum dynamical principles.

Work and free energy change

For a reversible isothermal process, ΔS = qrev/T and therefore the definition of A results in

(at constant temperature)

This tells us that the change in free energy equals the reversible or maximum work for a process performed at constant temperature. Under other conditions, free-energy change is not equal to work; for instance, for a reversible adiabatic expansion of an ideal gas, . Importantly, for a heat engine, including the Carnot cycle, the free-energy change after a full cycle is zero, , while the engine produces nonzero work. It is important to note that for heat engines and other thermal systems, the free energies do not offer convenient characterizations; internal energy and enthalpy are the preferred potentials for characterizing thermal systems.

Free energy change and spontaneous processes

According to the second law of thermodynamics, for any process that occurs in a closed system, the inequality of Clausius, ΔS > q/Tsurr, applies. For a process at constant temperature and pressure without non-PV work, this inequality transforms into . Similarly, for a process at constant temperature and volume, . Thus, a negative value of the change in free energy is a necessary condition for a process to be spontaneous; this is the most useful form of the second law of thermodynamics in chemistry. In chemical equilibrium at constant T and p without electrical work, dG = 0.

History

The quantity called "free energy" is a more advanced and accurate replacement for the outdated term affinity, which was used by chemists in previous years to describe the force that caused chemical reactions. The term affinity, as used in chemical relation, dates back to at least the time of Albertus Magnus. [13]

From the 1998 textbook Modern Thermodynamics [14] by Nobel Laureate and chemistry professor Ilya Prigogine we find: "As motion was explained by the Newtonian concept of force, chemists wanted a similar concept of ‘driving force’ for chemical change. Why do chemical reactions occur, and why do they stop at certain points? Chemists called the ‘force’ that caused chemical reactions affinity, but it lacked a clear definition."

During the entire 18th century, the dominant view with regard to heat and light was that put forth by Isaac Newton, called the Newtonian hypothesis, which states that light and heat are forms of matter attracted or repelled by other forms of matter, with forces analogous to gravitation or to chemical affinity.

In the 19th century, the French chemist Marcellin Berthelot and the Danish chemist Julius Thomsen had attempted to quantify affinity using heats of reaction. In 1875, after quantifying the heats of reaction for a large number of compounds, Berthelot proposed the principle of maximum work , in which all chemical changes occurring without intervention of outside energy tend toward the production of bodies or of a system of bodies which liberate heat.

In addition to this, in 1780 Antoine Lavoisier and Pierre-Simon Laplace laid the foundations of thermochemistry by showing that the heat given out in a reaction is equal to the heat absorbed in the reverse reaction. They also investigated the specific heat and latent heat of a number of substances, and amounts of heat given out in combustion. In a similar manner, in 1840 Swiss chemist Germain Hess formulated the principle that the evolution of heat in a reaction is the same whether the process is accomplished in one-step process or in a number of stages. This is known as Hess' law. With the advent of the mechanical theory of heat in the early 19th century, Hess's law came to be viewed as a consequence of the law of conservation of energy.

Based on these and other ideas, Berthelot and Thomsen, as well as others, considered the heat given out in the formation of a compound as a measure of the affinity, or the work done by the chemical forces. This view, however, was not entirely correct. In 1847, the English physicist James Joule showed that he could raise the temperature of water by turning a paddle wheel in it, thus showing that heat and mechanical work were equivalent or proportional to each other, i.e., approximately, dWdQ. This statement came to be known as the mechanical equivalent of heat and was a precursory form of the first law of thermodynamics.

By 1865, the German physicist Rudolf Clausius had shown that this equivalence principle needed amendment. That is, one can use the heat derived from a combustion reaction in a coal furnace to boil water, and use this heat to vaporize steam, and then use the enhanced high-pressure energy of the vaporized steam to push a piston. Thus, we might naively reason that one can entirely convert the initial combustion heat of the chemical reaction into the work of pushing the piston. Clausius showed, however, that we must take into account the work that the molecules of the working body, i.e., the water molecules in the cylinder, do on each other as they pass or transform from one step of or state of the engine cycle to the next, e.g., from () to (). Clausius originally called this the “transformation content” of the body, and then later changed the name to entropy. Thus, the heat used to transform the working body of molecules from one state to the next cannot be used to do external work, e.g., to push the piston. Clausius defined this transformation heat as .

In 1873, Willard Gibbs published A Method of Geometrical Representation of the Thermodynamic Properties of Substances by Means of Surfaces, in which he introduced the preliminary outline of the principles of his new equation able to predict or estimate the tendencies of various natural processes to ensue when bodies or systems are brought into contact. By studying the interactions of homogeneous substances in contact, i.e., bodies, being in composition part solid, part liquid, and part vapor, and by using a three-dimensional volume-entropy-internal energy graph, Gibbs was able to determine three states of equilibrium, i.e., "necessarily stable", "neutral", and "unstable", and whether or not changes will ensue. In 1876, Gibbs built on this framework by introducing the concept of chemical potential so to take into account chemical reactions and states of bodies that are chemically different from each other. In his own words, to summarize his results in 1873, Gibbs states:

If we wish to express in a single equation the necessary and sufficient condition of thermodynamic equilibrium for a substance when surrounded by a medium of constant pressure p and temperature T, this equation may be written:

δ(ε + ) = 0

when δ refers to the variation produced by any variations in the state of the parts of the body, and (when different parts of the body are in different states) in the proportion in which the body is divided between the different states. The condition of stable equilibrium is that the value of the expression in the parenthesis shall be a minimum.

In this description, as used by Gibbs, ε refers to the internal energy of the body, η refers to the entropy of the body, and ν is the volume of the body.

Hence, in 1882, after the introduction of these arguments by Clausius and Gibbs, the German scientist Hermann von Helmholtz stated, in opposition to Berthelot and Thomas’ hypothesis that chemical affinity is a measure of the heat of reaction of chemical reaction as based on the principle of maximal work, that affinity is not the heat given out in the formation of a compound but rather it is the largest quantity of work which can be gained when the reaction is carried out in a reversible manner, e.g., electrical work in a reversible cell. The maximum work is thus regarded as the diminution of the free, or available, energy of the system (Gibbs free energy G at T = constant, P = constant or Helmholtz free energy A at T = constant, V = constant), whilst the heat given out is usually a measure of the diminution of the total energy of the system (Internal energy). Thus, G or A is the amount of energy “free” for work under the given conditions.

Up until this point, the general view had been such that: “all chemical reactions drive the system to a state of equilibrium in which the affinities of the reactions vanish”. Over the next 60 years, the term affinity came to be replaced with the term free energy. According to chemistry historian Henry Leicester, the influential 1923 textbook Thermodynamics and the Free Energy of Chemical Reactions by Gilbert N. Lewis and Merle Randall led to the replacement of the term “affinity” by the term “free energy” in much of the English-speaking world.

See also

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 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 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">Second law of thermodynamics</span> Physical law for entropy and heat

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, unless energy is supplied to reverse the direction of heat flow. Another definition is: "Not all heat energy can be converted into work in a cyclic process."

In chemistry, the standard molar entropy is the entropy content of one mole of pure substance at a standard state of pressure and any temperature of interest. These are often chosen to be the standard temperature and pressure.

The Gibbs–Helmholtz equation is a thermodynamic equation used for calculating changes in the Gibbs free energy of a system as a function of temperature. It was originally presented in an 1882 paper entitled "Die Thermodynamik chemischer Vorgange" by Hermann von Helmholtz. It describes how the Gibbs free energy, which was presented originally by Josiah Willard Gibbs, varies with temperature.

In thermodynamics, the chemical potential of a species is the energy that can be absorbed or released due to a change of the particle number of the given species, e.g. in a chemical reaction or phase transition. The chemical potential of a species in a mixture is defined as the rate of change of free energy of a thermodynamic system with respect to the change in the number of atoms or molecules of the species that are added to the system. Thus, it is the partial derivative of the free energy with respect to the amount of the species, all other species' concentrations in the mixture remaining constant. When both temperature and pressure are held constant, and the number of particles is expressed in moles, the chemical potential is the partial molar Gibbs free energy. At chemical equilibrium or in phase equilibrium, the total sum of the product of chemical potentials and stoichiometric coefficients is zero, as the free energy is at a minimum. In a system in diffusion equilibrium, the chemical potential of any chemical species is uniformly the same everywhere throughout the system.

<span class="mw-page-title-main">Gibbs free energy</span> Type of thermodynamic potential; useful for calculating reversible work in certain systems

In thermodynamics, the Gibbs free energy is a thermodynamic potential that can be used to calculate the maximum amount of work that may be performed by a thermodynamically closed system at constant temperature and pressure. It also provides a necessary condition for processes such as chemical reactions that may occur under these conditions.

<span class="mw-page-title-main">Hess's law</span> Observation that total enthalpy change of a chemical reaction is independent of the steps taken

Hess's law of constant heat summation, also known simply as Hess' law, is a relationship in physical chemistry named after Germain Hess, a Swiss-born Russian chemist and physician who published it in 1840. The law states that the total enthalpy change during the complete course of a chemical reaction is independent of the sequence of steps taken.

<span class="mw-page-title-main">Thermodynamic potential</span> Scalar physical quantities representing system states

A thermodynamic potential is a scalar quantity used to represent the thermodynamic state of a system. The concept of thermodynamic potentials was introduced by Pierre Duhem in 1886. Josiah Willard Gibbs in his papers used the term fundamental functions.

<span class="mw-page-title-main">Helmholtz free energy</span> Thermodynamic potential

In thermodynamics, the Helmholtz free energy is a thermodynamic potential that measures the useful work obtainable from a closed thermodynamic system at a constant temperature (isothermal). The change in the Helmholtz energy during a process is equal to the maximum amount of work that the system can perform in a thermodynamic process in which temperature is held constant. At constant temperature, the Helmholtz free energy is minimized at equilibrium.

In thermodynamics, a spontaneous process is a process which occurs without any external input to the system. A more technical definition is the time-evolution of a system in which it releases free energy and it moves to a lower, more thermodynamically stable energy state. The sign convention for free energy change follows the general convention for thermodynamic measurements, in which a release of free energy from the system corresponds to a negative change in the free energy of the system and a positive change in the free energy of the surroundings.

<span class="mw-page-title-main">Internal energy</span> Energy contained within a system

The internal energy of a thermodynamic system is the energy contained within it. In an isolated system the internal energy is constant. It is the energy necessary to create or prepare the system in its given internal state. It does not include the kinetic energy of motion of the system as a whole, but it does include the kinetic energy of particles within the system. It keeps account of the gains and losses of energy of the system that are due to changes in its internal state. The internal energy cannot be measured directly. It is measured as a difference from a reference zero defined by a standard state. The difference is determined by thermodynamic processes that carry the system between the reference state and the given state of interest.

<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, 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 not thermodynamic systems. A wall of a thermodynamic system may be purely notional, when it is described as being 'permeable' to all matter, all radiation, and all forces. A state of a thermodynamic system can be fully described in several different ways, by several different sets of thermodynamic state variables.

<span class="mw-page-title-main">Endergonic reaction</span> Chemical reaction which requires more energy to initiate than it produces

In chemical thermodynamics, an endergonic reaction is a chemical reaction in which the standard change in free energy is positive, and an additional driving force is needed to perform this reaction. In layman's terms, the total amount of useful energy is negative so the total energy is a net negative result. For an overall gain in the net result, see exergonic reaction. Another way to phrase this is that useful energy must be absorbed from the surroundings into the workable system for the reaction to happen.

An exergonic process is one which there is a positive flow of energy from the system to the surroundings. This is in contrast with an endergonic process. Constant pressure, constant temperature reactions are exergonic if and only if the Gibbs free energy change is negative (∆G < 0). "Exergonic" means "releasing energy in the form of work". In thermodynamics, work is defined as the energy moving from the system to the surroundings during a given process.

<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.

The Van 't Hoff equation relates the change in the equilibrium constant, Keq, of a chemical reaction to the change in temperature, T, given the standard enthalpy change, ΔrH, for the process. It was proposed by Dutch chemist Jacobus Henricus van 't Hoff in 1884 in his book Études de Dynamique chimique.

<span class="mw-page-title-main">Fundamental thermodynamic relation</span>

In thermodynamics, the fundamental thermodynamic relation are four fundamental equations which demonstrate how four important thermodynamic quantities depend on variables that can be controlled and measured experimentally. Thus, they are essentially equations of state, and using the fundamental equations, experimental data can be used to determine sought-after quantities like G or H. The relation is generally expressed as a microscopic change in internal energy in terms of microscopic changes in entropy, and volume for a closed system in thermal equilibrium in the following way.

In the history of science, the principle of maximum work was a postulate concerning the relationship between chemical reactions, heat evolution, and the potential work produced there from. The principle was developed in approximate form in 1875 by French chemist Marcellin Berthelot, in the field of thermochemistry, and then in 1876 by American mathematical physicist Willard Gibbs, in the field of thermodynamics, in a more accurate form. Berthelot's version was essentially: "every pure chemical reaction is accompanied by evolution of heat.". The effects of irreversibility, however, showed this version to be incorrect. This was rectified, in thermodynamics, by incorporating the concept of entropy.

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

In thermodynamics, heat is defined as the form of energy crossing the boundary of a thermodynamic system by virtue of a temperature difference across the boundary. A thermodynamic system does not contain heat. Nevertheless, the term is also often used to refer to the thermal energy contained in a system as a component of its internal energy, and that is reflected in the temperature of the system. For example, Richard Feynman introduced heat with a physical description, the jiggling motion of atoms and molecules, with faster motion corresponding to increased temperature. To explain physics further, he used the term "heat energy," along with "heat". For both uses of the term, heat is a form of energy.

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