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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".
= , where k B is the Boltzmann constant, and Ω denotes the volume of macrostate in the phase space or otherwise called thermodynamic probability. d S = δ Q T {\displaystyle dS={\frac {\delta Q}{T}}} , for reversible processes only
The Boltzmann constant (k B or k) is the proportionality factor that relates the average relative thermal energy of particles in a gas with the thermodynamic temperature of the gas. [2] It occurs in the definitions of the kelvin (K) and the gas constant , in Planck's law of black-body radiation and Boltzmann's entropy formula , and is used in ...
‡ = entropy of activation; If one assumes constant enthalpy of activation, constant entropy of activation, and constant transmission coefficient, this equation can be used as follows: A certain chemical reaction is performed at different temperatures and the reaction rate is determined.
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 gas constant occurs in the ideal gas law: = = where P is the absolute pressure, V is the volume of gas, n is the amount of substance, m is the mass, and T is the thermodynamic temperature. R specific is the mass-specific gas constant. The gas constant is expressed in the same unit as molar heat.
for reactions in solution and unimolecular gas reactions A = (ek B T/h) exp(ΔS ‡ /R), while for bimolecular gas reactions A = (e 2 k B T/h) (RT/p) exp(ΔS ‡ /R). In these equations e is the base of natural logarithms, h is the Planck constant, k B is the Boltzmann constant and T the absolute temperature. R′ is the ideal gas constant. The ...
Mathematically, the absolute entropy of any system at zero temperature is the natural log of the number of ground states times the Boltzmann constant k B = 1.38 × 10 −23 J K −1. The entropy of a perfect crystal lattice as defined by Nernst's theorem is zero provided that its ground state is unique, because ln(1) = 0.