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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".
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 ...
Since an entropy is a state function, the entropy change of the system for an irreversible path is the same as for a reversible path between the same two states. [23] However, the heat transferred to or from the surroundings is different as well as its entropy change. We can calculate the change of entropy only by integrating the above formula.
Entropy of activation determines the preexponential factor A of the Arrhenius equation for temperature dependence of reaction rates. The relationship depends on the molecularity of the reaction: 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 ...
= , 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
Trouton’s rule can be explained by using Boltzmann's definition of entropy to the relative change in free volume (that is, space available for movement) between the liquid and vapour phases. [ 2 ] [ 3 ] It is valid for many liquids; for instance, the entropy of vaporization of toluene is 87.30 J/(K·mol), that of benzene is 89.45 J/(K·mol ...
Boltzmann's entropy formula—carved on his gravestone. [1]In statistical mechanics, Boltzmann's entropy formula (also known as the Boltzmann–Planck equation, not to be confused with the more general Boltzmann equation, which is a partial differential equation) is a probability equation relating the entropy, also written as , of an ideal gas to the multiplicity (commonly denoted as or ), 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.