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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".
It is assumed that the collected experimental data comprise a set of data points. At each i th data point, the analytical concentrations of the reactants, T A (i), T B (i) etc. are known along with a measured quantity, y i, that depends on one or more of these analytical concentrations. A general computational procedure has four main components:
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 ...
a thermodynamic equilibrium constant, denoted by , is defined to be the value of the reaction quotient Q t when forward and reverse reactions occur at the same rate. At chemical equilibrium , the chemical composition of the mixture does not change with time, and the Gibbs free energy change Δ G {\displaystyle \Delta G} for the reaction is zero.
The maximum work is thus regarded as the diminution of the free, or available, energy of the system (Gibbs free energy G at T = constant, P = constant or Helmholtz free energy F at T = constant, V = constant), whilst the heat given out is usually a measure of the diminution of the total energy of the system (internal energy).
In physical organic chemistry, a free-energy relationship or Gibbs energy relation relates the logarithm of a reaction rate constant or equilibrium constant for one series of chemical reactions with the logarithm of the rate or equilibrium constant for a related series of reactions. [1]
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 ...
In the following chemical equation, arrows point both ways to indicate equilibrium. [5] A and B are reactant chemical species, S and T are product species, and α, β, σ, and τ are the stoichiometric coefficients of the respective reactants and products: α A + β B ⇌ σ S + τ T