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Faraday discovered that when the same amount of electric current is passed through different electrolytes connected in series, the masses of the substances deposited or liberated at the electrodes are directly proportional to their respective chemical equivalent/equivalent weight (E). [3]
The standard state of a material (pure substance, mixture or solution) is a reference point used to calculate its properties under different conditions.A degree sign (°) or a superscript Plimsoll symbol (⦵) is used to designate a thermodynamic quantity in the standard state, such as change in enthalpy (ΔH°), change in entropy (ΔS°), or change in Gibbs free energy (ΔG°).
The Hammett equation predicts the equilibrium constant or reaction rate of a reaction from a substituent constant and a reaction type constant. The Edwards equation relates the nucleophilic power to polarisability and basicity. The Marcus equation is an example of a quadratic free-energy relationship (QFER). [citation needed]
In electrochemistry, the electrochemical potential of electrons (or any other species) is the total potential, including both the (internal, nonelectrical) chemical potential and the electric potential, and is by definition constant across a device in equilibrium, whereas the chemical potential of electrons is equal to the electrochemical ...
An alternative to free-energy perturbation for computing potentials of mean force in chemical space is thermodynamic integration. Another alternative, which is probably more efficient, is the Bennett acceptance ratio method. Adaptations to FEP exist which attempt to apportion free-energy changes to subsections of the chemical structure. [5]
Chemical potentials can be used to explain the slopes of lines on a phase diagram by using the Clapeyron equation, which in turn can be derived from the Gibbs–Duhem equation. [9] They are used to explain colligative properties such as melting-point depression by the application of pressure. [ 10 ]
Marcus' formula shows a quadratic dependence of the Gibbs free energy of activation on the Gibbs free energy of reaction. It is general knowledge from the host of chemical experience that reactions usually are the faster the more negative is . In many cases even a linear free energy relation is found.
The law states that the total enthalpy change during the complete course of a chemical reaction is independent of the sequence of steps taken. [2] [3] Hess's law is now understood as an expression of the fact that the enthalpy of a chemical process is independent of the path taken from the initial to the final state (i.e. enthalpy is a state ...