Thermodynamic Equations
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Thermodynamic Equations
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. Introduction One of the fundamental thermodynamic equations is the description of thermodynamic work in analogy to mechanical work, or weight lifted through an elevation against gravity, as defined in 1824 by French physicist Sadi Carnot. Carnot used the phrase motive power for work. In the footnotes to his famous ''On the Motive Power of Fire'', he states: “We use here the expression ''motive power'' to express the useful effect that a motor is capable of producing. This effect can always be likened to the elevation of a weight to a certain height. It has, as we know, as a measure, the product of the weight multiplied by the height to which it is raised.” With the inc ...
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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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First Law Of Thermodynamics
The first law of thermodynamics is a formulation of the law of conservation of energy, adapted for thermodynamic processes. It distinguishes in principle two forms of energy transfer, heat and thermodynamic work for a system of 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 energies in the system. The law of conservation of energy states that the total energy of any isolated system, which cannot exchange energy or matter, is constant. Energy can be transformed from one form to another, but can be neither created nor destroyed. The first law for a thermodynamic process is often formulated asThe sign convention (Q is heat supplied ''to'' the system but W is work done ''by'' the system) is that of Rudolf Clausius (Equation IIa on page 384 of Clausius, R. (1850)), and it is followed below. :\Delta U = Q - W, where \Delta U denotes the change in the internal energy of a closed system (f ...
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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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Enthalpy
Enthalpy , a property of a thermodynamic system, is the sum of the system's internal energy and the product of its pressure and volume. It is a state function used in many measurements in chemical, biological, and physical systems at a constant pressure, which is conveniently provided by the large ambient atmosphere. The pressure–volume term expresses the work required to establish the system's physical dimensions, i.e. to make room for it by displacing its surroundings. The pressure-volume term is very small for solids and liquids at common conditions, and fairly small for gases. Therefore, enthalpy is a stand-in for energy in chemical systems; bond, lattice, solvation and other "energies" in chemistry are actually enthalpy differences. As a state function, enthalpy depends only on the final configuration of internal energy, pressure, and volume, not on the path taken to achieve it. In the International System of Units (SI), the unit of measurement for enthalpy is the joule. ...
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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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Internal Energy
The internal energy of a thermodynamic system is the total energy contained within it. It is the energy necessary to create or prepare the system in its given internal state, and includes the contributions of potential energy and internal kinetic energy. It keeps account of the gains and losses of energy of the system that are due to changes in its internal state. It does not include the kinetic energy of motion of the system as a whole, or any external energies from surrounding force fields. The internal energy of an isolated system is constant, which is expressed as the law of conservation of energy, a foundation of the first law of thermodynamics. The internal energy is an extensive property. The internal energy cannot be measured directly and knowledge of all its components is rarely interesting, such as the static rest mass energy of its constituent matter. Thermodynamics is chiefly concerned only with ''changes'' in the internal energy, not with its absolute value. Instea ...
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Thermodynamic Potential
A thermodynamic potential (or more accurately, a thermodynamic potential energy)ISO/IEC 80000-5, Quantities an units, Part 5 - Thermodynamics, item 5-20.4 Helmholtz energy, Helmholtz functionISO/IEC 80000-5, Quantities an units, Part 5 - Thermodynamics, item 5-20.5, Gibbs energy, Gibbs function 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''. One main thermodynamic potential that has a physical interpretation is the internal energy . It is the energy of configuration of a given system of conservative forces (that is why it is called potential) and only has meaning with respect to a defined set of references (or data). Expressions for all other thermodynamic energy potentials are derivable via Legendre transforms from an expression for . In thermodynamics, external forces, such as gravity, are c ...
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Particle Number
The particle number (or number of particles) of a thermodynamic system, conventionally indicated with the letter ''N'', is the number of constituent particles in that system. The particle number is a fundamental parameter in thermodynamics which is conjugate to the chemical potential. Unlike most physical quantities, particle number is a dimensionless quantity. It is an extensive parameter, as it is directly proportional to the size of the system under consideration, and thus meaningful only for closed systems. A constituent particle is one that cannot be broken into smaller pieces at the scale of energy ''k·T'' involved in the process (where ''k'' is the Boltzmann constant and ''T'' is the temperature). For example, for a thermodynamic system consisting of a piston containing water vapour, the particle number is the number of water molecules in the system. The meaning of constituent particle, and thereby of particle number, is thus temperature-dependent. Determining the particle ...
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Chemical Potential
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, th ...
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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 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. The thermodynamic concept was referred to by Scottish scientist and engineer William Rankine in 1850 with the names ''thermodynamic function'' and ''heat-potential''. In 1865, German physicist Rudolf Clausius, one of the leading founders of the field of thermodynamics, defined it as the quotient of an infinitesimal amount of hea ...
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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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Volume
Volume is a measure of occupied three-dimensional space. It is often quantified numerically using SI derived units (such as the cubic metre and litre) or by various imperial or US customary units (such as the gallon, quart, cubic inch). The definition of length (cubed) is interrelated with volume. The volume of a container is generally understood to be the capacity of the container; i.e., the amount of fluid (gas or liquid) that the container could hold, rather than the amount of space the container itself displaces. In ancient times, volume is measured using similar-shaped natural containers and later on, standardized containers. Some simple three-dimensional shapes can have its volume easily calculated using arithmetic formulas. Volumes of more complicated shapes can be calculated with integral calculus if a formula exists for the shape's boundary. Zero-, one- and two-dimensional objects have no volume; in fourth and higher dimensions, an analogous concept to the normal vo ...
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