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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.
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]
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.
In physical chemistry, the Arrhenius equation is a formula for the temperature dependence of reaction rates.The equation was proposed by Svante Arrhenius in 1889, based on the work of Dutch chemist Jacobus Henricus van 't Hoff who had noted in 1884 that the van 't Hoff equation for the temperature dependence of equilibrium constants suggests such a formula for the rates of both forward and ...
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 ...
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 ...
Equilibrium chemistry is concerned with systems in chemical equilibrium.The unifying principle is that the free energy of a system at equilibrium is the minimum possible, so that the slope of the free energy with respect to the reaction coordinate is zero.
The reaction proceeds in the forward direction (towards larger values of Q r) when Δ r G < 0 or in the reverse direction (towards smaller values of Q r) when Δ r G > 0. Eventually, as the reaction mixture reaches chemical equilibrium, the activities of the components (and thus the reaction quotient) approach constant values.