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The Van 't Hoff equation relates the change in the equilibrium constant, K eq, of a chemical reaction to the change in temperature, T, given the standard enthalpy change, Δ r H ⊖, for the process. The subscript r {\displaystyle r} means "reaction" and the superscript ⊖ {\displaystyle \ominus } means "standard".
For a given set of reaction conditions, the equilibrium constant is independent of the initial analytical concentrations of the reactant and product species in the mixture. Thus, given the initial composition of a system, known equilibrium constant values can be used to determine the composition of the system at 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 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 ...
In thermodynamics, the Gibbs free energy (or Gibbs energy as the recommended name; symbol ) is a thermodynamic potential that can be used to calculate the maximum amount of work, other than pressure–volume work, that may be performed by a thermodynamically closed system at constant temperature and pressure.
Where this is not possible, consideration should be given to possible activity variation. The equilibrium expression above is a function of the concentrations [A], [B] etc. of the chemical species in equilibrium. The equilibrium constant value can be determined if any one of these concentrations can be measured.
The definition of the Gibbs function is = + where H is the enthalpy defined by: = +. Taking differentials of each definition to find dH and dG, then using the fundamental thermodynamic relation (always true for reversible or irreversible processes): = where S is the entropy, V is volume, (minus sign due to reversibility, in which dU = 0: work other than pressure-volume may be done and is equal ...
Thus, G or A is the amount of energy "free" for work under the given conditions. Up until this point, the general view had been such that: “all chemical reactions drive the system to a state of equilibrium in which the affinities of the reactions vanish”. Over the next 60 years, the term affinity came to be replaced with the term free energy.
CH 3 CO 2 H + H 2 O ⇌ CH 3 CO − 2 + H 3 O + a proton may hop from one molecule of acetic acid onto a water molecule and then onto an acetate anion to form another molecule of acetic acid and leaving the number of acetic acid molecules unchanged. This is an example of dynamic equilibrium. Equilibria, like the rest of thermodynamics, are ...