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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".
is the gas constant and is the absolute temperature. The volume fraction is analogous to the mole fraction , but is weighted to take account of the relative sizes of the molecules. For a small solute, the mole fractions would appear instead, and this modification is the innovation due to Flory and Huggins.
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 ...
In thermodynamics, the entropy of mixing is the increase in the total entropy when several initially separate systems of different composition, each in a thermodynamic state of internal equilibrium, are mixed without chemical reaction by the thermodynamic operation of removal of impermeable partition(s) between them, followed by a time for establishment of a new thermodynamic state of internal ...
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 ...
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.
The above change in composition is in accordance with Le Chatelier's principle and does not involve any change of the equilibrium constant with the total system pressure. Indeed, for ideal-gas reactions K p is independent of pressure. [17] Pressure dependence of the water ionization constant at 25 °C.
In thermodynamics, enthalpy–entropy compensation is a specific example of the compensation effect. The compensation effect refers to the behavior of a series of closely related chemical reactions (e.g., reactants in different solvents or reactants differing only in a single substituent), which exhibit a linear relationship between one of the following kinetic or thermodynamic parameters for ...