Thermodynamic Free Energy
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Thermodynamic Free Energy
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. 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. Since first-law energy is always conserved, it is evident that free energy ...
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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 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. 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. Scots-Irish physicist Lord Kelvin was the first to formulate a ...
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Gibbs Free Energy
In thermodynamics, the Gibbs free energy (or Gibbs energy; symbol G) 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. The Gibbs free energy change , measured in joules in SI) is the ''maximum'' amount of non-expansion work that can be extracted from a closed system (one that can exchange heat and work with its surroundings, but not matter) at fixed temperature and pressure. This maximum can be attained only in a completely reversible process. When a system transforms reversibly from an initial state to a final state under these conditions, the decrease in Gibbs free energy equals the work done by the system to its surroundings, minus the work of the pressure forces. The Gibbs energy is the thermodynamic potential that is minim ...
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Canonical Ensemble
In statistical mechanics, a canonical ensemble is the statistical ensemble that represents the possible states of a mechanical system in thermal equilibrium with a heat bath at a fixed temperature. The system can exchange energy with the heat bath, so that the states of the system will differ in total energy. The principal thermodynamic variable of the canonical ensemble, determining the probability distribution of states, is the absolute temperature (symbol: ). The ensemble typically also depends on mechanical variables such as the number of particles in the system (symbol: ) and the system's volume (symbol: ), each of which influence the nature of the system's internal states. An ensemble with these three parameters is sometimes called the ensemble. The canonical ensemble assigns a probability to each distinct microstate given by the following exponential: :P = e^, where is the total energy of the microstate, and is the Boltzmann constant. The number is the free ener ...
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Partition Function (statistical Mechanics)
In physics, a partition function describes the statistical properties of a system in thermodynamic equilibrium. Partition functions are functions of the thermodynamic state variables, such as the temperature and volume. Most of the aggregate thermodynamic variables of the system, such as the total energy, free energy, entropy, and pressure, can be expressed in terms of the partition function or its derivatives. The partition function is dimensionless. Each partition function is constructed to represent a particular statistical ensemble (which, in turn, corresponds to a particular free energy). The most common statistical ensembles have named partition functions. The canonical partition function applies to a canonical ensemble, in which the system is allowed to exchange heat with the environment at fixed temperature, volume, and number of particles. The grand canonical partition function applies to a grand canonical ensemble, in which the system can exchange both heat and p ...
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Logarithm
In mathematics, the logarithm is the inverse function to exponentiation. That means the logarithm of a number  to the base  is the exponent to which must be raised, to produce . For example, since , the ''logarithm base'' 10 of is , or . The logarithm of to ''base''  is denoted as , or without parentheses, , or even without the explicit base, , when no confusion is possible, or when the base does not matter such as in big O notation. The logarithm base is called the decimal or common logarithm and is commonly used in science and engineering. The natural logarithm has the number  as its base; its use is widespread in mathematics and physics, because of its very simple derivative. The binary logarithm uses base and is frequently used in computer science. Logarithms were introduced by John Napier in 1614 as a means of simplifying calculations. They were rapidly adopted by navigators, scientists, engineers, surveyors and others to perform high-a ...
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Theory
A theory is a rational type of abstract thinking about a phenomenon, or the results of such thinking. The process of contemplative and rational thinking is often associated with such processes as observational study or research. Theories may be scientific, belong to a non-scientific discipline, or no discipline at all. Depending on the context, a theory's assertions might, for example, include generalized explanations of how nature works. The word has its roots in ancient Greek, but in modern use it has taken on several related meanings. In modern science, the term "theory" refers to scientific theories, a well-confirmed type of explanation of nature, made in a way consistent with the scientific method, and fulfilling the criteria required by modern science. Such theories are described in such a way that scientific tests should be able to provide empirical support for it, or empirical contradiction ("falsify") of it. Scientific theories are the most reliable, rigorous, and compr ...
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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 entire reversible process, the system is in thermodynamic equilibrium, both physical and chemical, and ''nearly'' in pressure and temperature equilibrium with its surroundings. This prevents unbalanced forces and acceleration of moving system boundaries, which in turn avoids friction and other dissipation. To maintain equilibrium, reversible processes are extremely slow ( ''quasistatic''). The process must occur slowly enough that after some small change in a thermodynamic parameter, the physical processes in the system have enough time for the other parameters to self-adjust to match the new, changed parameter value. For example, if a container of water has sat in a room long enough to match the steady temperature of the surrounding air, for ...
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Helmholtz Free Energy
In thermodynamics, the Helmholtz free energy (or Helmholtz energy) is a thermodynamic potential that measures the useful work obtainable from a closed thermodynamic system at a constant temperature (isothermal In thermodynamics, an isothermal process is a type of thermodynamic process in which the temperature ''T'' of a system remains constant: Δ''T'' = 0. This typically occurs when a system is in contact with an outside thermal reservoir, and ...). 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 contrast, the Gibbs free energy or free enthalpy is most commonly used as a measure of thermodynamic potential (especially in chemistry) when it is convenient for applications that occur at constant ''pressure''. For example, in explosives research Helmholtz ...
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Phase (matter)
In the physical sciences, a phase is a region of space (a thermodynamic system), throughout which all physical properties of a material are essentially uniform. Examples of physical properties include density, index of refraction, magnetization and chemical composition. A simple description is that a phase is a region of material that is chemically uniform, physically distinct, and (often) mechanically separable. In a system consisting of ice and water in a glass jar, the ice cubes are one phase, the water is a second phase, and the humid air is a third phase over the ice and water. The glass of the jar is another separate phase. (See ) The term ''phase'' is sometimes used as a synonym for state of matter, but there can be several immiscible phases of the same state of matter. Also, the term ''phase'' is sometimes used to refer to a set of equilibrium states demarcated in terms of state variables such as pressure and temperature by a phase boundary on a phase diagram. Bec ...
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Solution (chemistry)
In chemistry, a solution is a special type of homogeneous mixture composed of two or more substances. In such a mixture, a solute is a substance dissolved in another substance, known as a solvent. If the attractive forces between the solvent and solute particles are greater than the attractive forces holding the solute particles together, the solvent particles pull the solute particles apart and surround them. These surrounded solute particles then move away from the solid solute and out into the solution. The mixing process of a solution happens at a scale where the effects of chemical polarity are involved, resulting in interactions that are specific to solvation. The solution usually has the state of the solvent when the solvent is the larger fraction of the mixture, as is commonly the case. One important parameter of a solution is the concentration, which is a measure of the amount of solute in a given amount of solution or solvent. The term "aqueous solution" is used when ...
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Heat
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 both uses of the term, heat is a form of energy. An example of formal vs. informal usage may be obtained from the right-hand photo, in which the metal bar is "conducting heat" from its hot end to its cold end, but if the metal bar is considered a thermodynamic system, then the energy flowing within the metal bar is called internal energy, not heat. The hot metal bar is also transferring heat to its surroundings, a correct statement for both the strict and loose meanings of ''heat''. Another example of informal usage is the term '' heat content'', used despite the fact that p ...
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Temperature
Temperature is a physical quantity that expresses quantitatively the perceptions of hotness and coldness. Temperature is measured with a thermometer. Thermometers are calibrated in various temperature scales that historically have relied on various reference points and thermometric substances for definition. The most common scales are the Celsius scale with the unit symbol °C (formerly called ''centigrade''), the Fahrenheit scale (°F), and the Kelvin scale (K), the latter being used predominantly for scientific purposes. The kelvin is one of the seven base units in the International System of Units (SI). Absolute zero, i.e., zero kelvin or −273.15 °C, is the lowest point in the thermodynamic temperature scale. Experimentally, it can be approached very closely but not actually reached, as recognized in the third law of thermodynamics. It would be impossible to extract energy as heat from a body at that temperature. Temperature is important in all fields of natur ...
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