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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.
When two or more sites in an asymmetrical molecule may be involved in an equilibrium reaction there are more than one possible equilibrium constants. For example, the molecule L-DOPA has two non-equivalent hydroxyl groups which may be deprotonated. Denoting L-DOPA as LH 2, the following diagram shows all the species that may be formed (X = CH 2 ...
There are two approaches to the calculation of the unknown molar absorptivities (1) The ε values are considered parameters of the minimization and the Jacobian is constructed on that basis. However, the ε values themselves are calculated at each step of the refinement by linear least-squares:
In physical organic chemistry, a free-energy relationship or Gibbs energy relation relates the logarithm of a reaction rate constant or equilibrium constant for one series of chemical reactions with the logarithm of the rate or equilibrium constant for a related series of reactions. [1]
The reversible reaction N 2 O 4 (g) ⇌ 2NO 2 (g) is endothermic, so the equilibrium position can be shifted by changing the temperature. When heat is added and the temperature increases, the reaction shifts to the right and the flask turns reddish brown due to an increase in NO 2. This demonstrates Le Chatelier's principle: the equilibrium ...
Using the Eyring equation, there is a straightforward relationship between ΔG ‡, first-order rate constants, and reaction half-life at a given temperature. At 298 K, a reaction with ΔG ‡ = 23 kcal/mol has a rate constant of k ≈ 8.4 × 10 −5 s −1 and a half life of t 1/2 ≈ 2.3 hours, figures that are often rounded to k ~ 10 −4 s ...
For instance, in the case of a dibasic acid, H 2 A dissolved in water the two reactants can be specified as the conjugate base, A 2−, and the proton, H +. The following equations of mass-balance could apply equally well to a base such as 1,2-diaminoethane, in which case the base itself is designated as the reactant A:
Some multistep reactions can also have apparent negative activation energies. For example, the overall rate constant k for a two-step reaction A ⇌ B, B → C is given by k = k 2 K 1, where k 2 is the rate constant of the rate-limiting slow second step and K 1 is the equilibrium constant of the rapid