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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".
An example is a hydrogen atom abstraction reaction R' + H–R ⇌ R'–H + R with equilibrium constant K H, where R' and R are organic radicals such that R' forms a stronger bond to hydrogen than does R.
Example: the pK a of the hydroxyl group in citric acid has been determined from 13 C chemical shift data to be 14.4. ... and the equilibrium constant, K, is defined ...
Most commonly [OH −] is replaced by K w [H +] −1 in equilibrium constant expressions which would otherwise include hydroxide ion. Solids also do not appear in the equilibrium constant expression, if they are considered to be pure and thus their activities taken to be one. An example is the Boudouard reaction: [14] 2 CO ⇌ CO 2 + C
The thermodynamic equilibrium constant, K ⊖, for the equilibrium + can be defined [15] as = {} {} {} where {ML} is the activity of the chemical species ML etc. K ⊖ is dimensionless since activity is dimensionless. Activities of the products are placed in the numerator, activities of the reactants are placed in the denominator.
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 −1 and t 1/2 ~ 2 h. Thus, a free energy of activation of this magnitude corresponds to a typical reaction that proceeds to completion overnight at room ...
The affinity constants, k + and k −, of the 1879 paper can now be recognised as rate constants. The equilibrium constant, K, was derived by setting the rates of forward and backward reactions to be equal. This also meant that the chemical affinities for the forward and backward reactions are equal. The resultant expression
where: k 1 is the rate coefficient for the reaction that consumes A and B; k −1 is the rate coefficient for the backwards reaction, which consumes P and Q and produces A and B. The constants k 1 and k −1 are related to the equilibrium coefficient for the reaction (K) by the following relationship (set v=0 in balance):