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Bordwell Thermodynamic Cycle
A Bordwell thermodynamic cycle use experimentally determined and reasonable estimates of Gibbs free energy (ΔG˚) values to determine unknown and experimentally inaccessible values. Overview Analogous to Hess's Law which deal with the summation of enthalpy (ΔH) values, Bordwell thermodynamic cycles deal with the summation of Gibbs free energy (ΔG) values. Free energies used in these systems are most often determined from equilibriums and redox potentials, both of which correlate with free energy. This is with the caveat that redox scales are not absolute and thus it is important that all electrons are evaluated in redox pairs. This removes the offset of a given reference potential, otherwise the values are reported as potentials (V) against that reference. It is also worth recognizing that the values of the pKa system are just moderately transformed Keq values. When working with equilibrium energy values such as ΔG˚ and E˚1/2 values it common to employ a naught (˚) ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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 ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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. ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Chemical Equilibrium
In a chemical reaction, chemical equilibrium is the state in which both the reactants and products are present in concentrations which have no further tendency to change with time, so that there is no observable change in the properties of the system. This state results when the forward reaction proceeds at the same rate as the reverse reaction. The reaction rates of the forward and backward reactions are generally not zero, but they are equal. Thus, there are no net changes in the concentrations of the reactants and products. Such a state is known as dynamic equilibrium. Historical introduction The concept of chemical equilibrium was developed in 1803, after Berthollet found that some chemical reactions are reversible. For any reaction mixture to exist at equilibrium, the rates of the forward and backward (reverse) reactions must be equal. In the following chemical equation, arrows point both ways to indicate equilibrium. A and B are reactant chemical species, S and T are p ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Redox Potential
Redox potential (also known as oxidation / reduction potential, ''ORP'', ''pe'', ''E_'', or E_) is a measure of the tendency of a chemical species to acquire electrons from or lose electrons to an electrode and thereby be reduced or oxidised respectively. Redox potential is expressed in volts (V). Each species has its own intrinsic redox potential; for example, the more positive the reduction potential (reduction potential is more often used due to general formalism in electrochemistry), the greater the species' affinity for electrons and tendency to be reduced. Measurement and interpretation In aqueous solutions, redox potential is a measure of the tendency of the solution to either gain or lose electrons when it is subjected to change by introduction of a new species. A solution with a higher (more positive) reduction potential than the new species will have a tendency to gain electrons from the new species (i.e. to be reduced by oxidizing the new species) and a solution with ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Activation Energy
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 (''E''a) 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 (sometimes called the energy 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. Other uses Although less commonly used, activation energy also applies to nuclear reactions and various other physical phenomena. Te ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Transition State
In chemistry, the transition state of a chemical reaction is a particular configuration along the reaction coordinate. It is defined as the state corresponding to the highest potential energy along this reaction coordinate. It is often marked with the double dagger ‡ symbol. As an example, the transition state shown below occurs during the SN2 reaction of bromoethane with a hydroxide anion: The activated complex of a reaction can refer to either the transition state or to other states along the reaction coordinate between reactants and products, especially those close to the transition state.Peter Atkins and Julio de Paula, ''Physical Chemistry'' (8th ed., W.H. Freeman 2006), p.809 According to the transition state theory, once the reactants have passed through the transition state configuration, they always continue to form products. History of concept The concept of a transition state has been important in many theories of the rates at which chemical reactions occ ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Bond Dissociation Energy
The bond-dissociation energy (BDE, ''D''0, or ''DH°'') is one measure of the strength of a chemical bond . It can be defined as the standard enthalpy change when is cleaved by homolysis to give fragments A and B, which are usually radical species. The enthalpy change is temperature-dependent, and the bond-dissociation energy is often defined to be the enthalpy change of the homolysis at 0 K (absolute zero), although the enthalpy change at 298 K (standard conditions) is also a frequently encountered parameter. As a typical example, the bond-dissociation energy for one of the C−H bonds in ethane () is defined as the standard enthalpy change of the process : , : ''DH''°298() = Δ''H°'' = 101.1(4) kcal/mol = 423.0 ± 1.7 kJ/mol = 4.40(2) eV (per bond). To convert a molar BDE to the energy needed to dissociate the bond ''per molecule'', the conversion factor 23.060 kcal/mol (96.485 kJ/mol) for each eV can be used. A variety of experim ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
