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log 10 β values between about 2 and 11 can be measured directly by potentiometric titration using a glass electrode. This enormous range of stability constant values (ca. 100 to 10 11) is possible because of the logarithmic response of the electrode. The limitations arise because the Nernst equation breaks down at very low or very high pH.
The value of an equilibrium constant determined in this manner is dependent on the ionic strength. When published constants refer to an ionic strength other than the one required for a particular application, they may be adjusted by means of specific ion theory (SIT) and other theories. [11]
where ln denotes the natural logarithm, is the thermodynamic equilibrium constant, and R is the ideal gas constant.This equation is exact at any one temperature and all pressures, derived from the requirement that the Gibbs free energy of reaction be stationary in a state of chemical equilibrium.
In physical chemistry and chemical engineering, extent of reaction is a quantity that measures the extent to which the reaction has proceeded. Often, it refers specifically to the value of the extent of reaction when equilibrium has been reached. It is usually denoted by the Greek letter ξ.
These so-called activation parameters give insight into the nature of a transition state, including energy content and degree of order, compared to the starting materials and has become a standard tool for elucidation of reaction mechanisms in physical organic chemistry. The free energy of activation, ΔG ‡, is defined in transition state ...
In organic chemistry, the Hammett equation describes a linear free-energy relationship relating reaction rates and equilibrium constants for many reactions involving benzoic acid derivatives with meta- and para-substituents to each other with just two parameters: a substituent constant and a reaction constant.
Free energy relationships establish the extent at which bond formation and breakage happen in the transition state of a reaction, and in combination with kinetic isotope experiments a reaction mechanism can be determined. Free energy relationships are often used to calculate equilibrium constants since they are experimentally difficult to ...
The standard Gibbs energy change, together with the Gibbs energy of mixing, determine the equilibrium state. [8] [9] In this article only the constant pressure case is considered. The relation between the Gibbs free energy and the equilibrium constant can be found by considering chemical potentials. [1]