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.
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 chemistry and physics, activation energy is the minimum amount of energy that must be provided for compounds to result in a chemical reaction. The activation energy (Ea) of a reaction is measured in joules per mole (J/mol), kilojoules per mole (kJ/mol) or kilocalories per mole (kcal/mol). Activation energy can be thought of as the magnitude of the potential barrier separating minima of the potential energy surface pertaining to the initial and final thermodynamic state. For a chemical reaction to proceed at a reasonable rate, the temperature of the system should be high enough such that there exists an appreciable number of molecules with translational energy equal to or greater than the activation energy. The term "activation energy" was introduced in 1889 by the Swedish scientist Svante Arrhenius.
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 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 Nernst heat theorem was formulated by Walther Nernst early in the twentieth century and was used in the development of the third law of thermodynamics.
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 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.
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.
In thermodynamics, an isothermal process is a type of thermodynamic process in which the temperature T of a system remains constant: ΔT = 0. This typically occurs when a system is in contact with an outside thermal reservoir, and a change in the system occurs slowly enough to allow the system to be continuously adjusted to the temperature of the reservoir through heat exchange. In contrast, an adiabatic process is where a system exchanges no heat with its surroundings (Q = 0).
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.
An Ellingham diagram is a graph showing the temperature dependence of the stability of compounds. This analysis is usually used to evaluate the ease of reduction of metal oxides and sulfides. These diagrams were first constructed by Harold Ellingham in 1944. In metallurgy, the Ellingham diagram is used to predict the equilibrium temperature between a metal, its oxide, and oxygen — and by extension, reactions of a metal with sulfur, nitrogen, and other non-metals. The diagrams are useful in predicting the conditions under which an ore will be reduced to its metal. The analysis is thermodynamic in nature and ignores reaction kinetics. Thus, processes that are predicted to be favourable by the Ellingham diagram can still be slow.
In thermodynamics, entropy is a numerical quantity that shows that many physical processes can go in only one direction in time. For example, you can pour cream into coffee and mix it, but you cannot "unmix" it; you can burn a piece of wood, but you cannot "unburn" it. The word 'entropy' has entered popular usage to refer a lack of order or predictability, or of a gradual decline into disorder. A more physical interpretation of thermodynamic entropy refers to spread of energy or matter, or to extent and diversity of microscopic motion.
Thermodynamic databases contain information about thermodynamic properties for substances, the most important being enthalpy, entropy, and Gibbs free energy. Numerical values of these thermodynamic properties are collected as tables or are calculated from thermodynamic datafiles. Data is expressed as temperature-dependent values for one mole of substance at the standard pressure of 101.325 kPa, or 100 kPa. Unfortunately, both of these definitions for the standard condition for pressure are in use.
In chemistry, transition state theory (TST) explains the reaction rates of elementary chemical reactions. The theory assumes a special type of chemical equilibrium (quasi-equilibrium) between reactants and activated transition state complexes.
Nucleic acid thermodynamics is the study of how temperature affects the nucleic acid structure of double-stranded DNA (dsDNA). The melting temperature (Tm) is defined as the temperature at which half of the DNA strands are in the random coil or single-stranded (ssDNA) state. Tm depends on the length of the DNA molecule and its specific nucleotide sequence. DNA, when in a state where its two strands are dissociated, is referred to as having been denatured by the high temperature.
Enthalpy–entropy compensation is a specific example of the compensation effect. The compensation effect refers to the behavior of a series of closely related chemical reactions, which exhibit a linear relationship between one of the following kinetic or thermodynamic parameters for describing the reactions:
Thermochemical cycles combine solely heat sources (thermo) with chemical reactions to split water into its hydrogen and oxygen components. The term cycle is used because aside of water, hydrogen and oxygen, the chemical compounds used in these processes are continuously recycled.
