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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.
Jannik Bjerrum (son of Niels Bjerrum) developed the first general method for the determination of stability constants of metal-ammine complexes in 1941. [1] The reasons why this occurred at such a late date, nearly 50 years after Alfred Werner had proposed the correct structures for coordination complexes, have been summarised by Beck and Nagypál. [2]
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 Δ G ‡ = 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 ...
The relationship between a species' concentration and the measured quantity is specific for the measurement technique, as indicated in each section above. Using this relationship, the set of parameters, the stability constant values and values of properties such as molar absorptivity or specified chemical shifts, may be refined by a non-linear ...
As an example, consider the gas-phase reaction NO 2 + CO → NO + CO 2.If this reaction occurred in a single step, its reaction rate (r) would be proportional to the rate of collisions between NO 2 and CO molecules: r = k[NO 2][CO], where k is the reaction rate constant, and square brackets indicate a molar concentration.
The equilibrium constant of a chemical reaction is the value of its reaction quotient at chemical equilibrium, a state approached by a dynamic chemical system after sufficient time has elapsed at which its composition has no measurable tendency towards further change.
Its symbol is Δ f G˚. All elements in their standard states (diatomic oxygen gas, graphite, etc.) have standard Gibbs free energy change of formation equal to zero, as there is no change involved. Δ f G = Δ f G˚ + RT ln Q f, where Q f is the reaction quotient. At equilibrium, Δ f G = 0, and Q f = K, so the equation becomes Δ f G˚ = − ...
The value of ΔS ‡ provides clues about the molecularity of the rate determining step in a reaction, i.e. the number of molecules that enter this step. [2] Positive values suggest that entropy increases upon achieving the transition state, which often indicates a dissociative mechanism in which the activated complex is loosely bound and about ...