Chemical thermodynamicsChemical 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. The structure of chemical thermodynamics is based on the first two laws of thermodynamics.
ThermodynamicsThermodynamics 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.
Laws of thermodynamicsThe 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.
Gibbs free energyIn thermodynamics, the Gibbs free energy (or Gibbs energy as the recommended name; symbol ) is a thermodynamic potential that can be used to calculate the maximum amount of work, other than pressure-volume 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 is expressed as where p is pressure, T is the temperature, U is the internal energy, V is volume, H is the enthalpy, and S is the entropy.
EntropyEntropy 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.
Chemical potentialIn 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.
Non-equilibrium thermodynamicsNon-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 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.
Thermodynamic free energyIn thermodynamics, the thermodynamic free energy is one of the state functions of a thermodynamic system (the others being internal energy, enthalpy, entropy, etc.). 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.
First law of thermodynamicsThe first law of thermodynamics is a formulation of the law of conservation of energy, adapted for thermodynamic processes. A simple formulation is: "The total energy in a system remains constant, although it may be converted from one form to another." Another common phrasing is that "energy can neither be created nor destroyed". While there are many subtleties and implications that may be more precisely captured in more complex formulations, this is the essential principle of the First Law.
Second law of thermodynamicsThe 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"), unless energy in some form 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." The second law of thermodynamics in other versions establishes the concept of entropy as a physical property of a thermodynamic system.
Helmholtz free energyIn 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). 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.
EnthalpyEnthalpy ˈɛnθəlpi, 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.
Chemical reactionA chemical reaction is a process that leads to the chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the positions of electrons in the forming and breaking of chemical bonds between atoms, with no change to the nuclei (no change to the elements present), and can often be described by a chemical equation. Nuclear chemistry is a sub-discipline of chemistry that involves the chemical reactions of unstable and radioactive elements where both electronic and nuclear changes can occur.
Chemical energyChemical energy is the energy of chemical substances that is released when the substances undergo a chemical reaction and transform into other substances. Some examples of storage media of chemical energy include batteries, food, and gasoline (as well as oxygen gas, which is of high chemical energy due to its relatively weak double bond and indispensable for chemical-energy release in gasoline combustion). Breaking and re-making chemical bonds involves energy, which may be either absorbed by or evolved from a chemical system.
ChemistryChemistry is the scientific study of the properties and behavior of matter. It is a physical science under natural sciences that covers the elements that make up matter to the compounds made of atoms, molecules and ions: their composition, structure, properties, behavior and the changes they undergo during a reaction with other substances. Chemistry also addresses the nature of chemical bonds in chemical compounds. In the scope of its subject, chemistry occupies an intermediate position between physics and biology.
ElectrochemistryElectrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential difference as an outcome of a particular chemical change, or vice versa. These reactions involve electrons moving via an electronically-conducting phase (typically an external electrical circuit, but not necessarily, as in electroless plating) between electrodes separated by an ionically conducting and electronically insulating electrolyte (or ionic species in a solution).
Chemical kineticsChemical kinetics, also known as reaction kinetics, is the branch of physical chemistry that is concerned with understanding the rates of chemical reactions. It is different from chemical thermodynamics, which deals with the direction in which a reaction occurs but in itself tells nothing about its rate. Chemical kinetics includes investigations of how experimental conditions influence the speed of a chemical reaction and yield information about the reaction's mechanism and transition states, as well as the construction of mathematical models that also can describe the characteristics of a chemical reaction.
Entropy (statistical thermodynamics)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 microstates that constitute thermodynamic systems.
Standard enthalpy of reactionThe standard enthalpy of reaction (denoted ) for a chemical reaction is the difference between total reactant and total product molar enthalpies, calculated for substances in their standard states. This can in turn be used to predict the total chemical bond energy liberated or bound during reaction, as long as the enthalpy of mixing is also accounted for. For a generic chemical reaction the standard enthalpy of reaction is related to the standard enthalpy of formation values of the reactants and products by the following equation: In this equation, and are the stoichiometric coefficients of each product and reactant.
Entropy (information theory)In information theory, the entropy of a random variable is the average level of "information", "surprise", or "uncertainty" inherent to the variable's possible outcomes. Given a discrete random variable , which takes values in the alphabet and is distributed according to : where denotes the sum over the variable's possible values. The choice of base for , the logarithm, varies for different applications. Base 2 gives the unit of bits (or "shannons"), while base e gives "natural units" nat, and base 10 gives units of "dits", "bans", or "hartleys".
