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When pressure and temperature are variable, only of components have independent values for chemical potential and Gibbs' phase rule follows. The Gibbs−Duhem equation applies to homogeneous thermodynamic systems. It does not apply to inhomogeneous systems such as small thermodynamic systems, [2], systems subject to long-range forces like ...
Hence, the main functional application of Gibbs energy from a thermodynamic database is its change in value during the formation of a compound from the standard-state elements, or for any standard chemical reaction (ΔG° form or ΔG° rx). The SI units of Gibbs energy are the same as for enthalpy (J/mol).
The concept of thermodynamic potentials was introduced by Pierre Duhem in 1886. Josiah Willard Gibbs in his papers used the term fundamental functions. Effects of changes in thermodynamic potentials can sometimes be measured directly, while their absolute magnitudes can only be assessed using computational chemistry or similar methods. [3]
Differentiating the Euler equation for the internal energy and combining with the fundamental equation for internal energy, it follows that: = + which is known as the Gibbs-Duhem relationship. The Gibbs-Duhem is a relationship among the intensive parameters of the system.
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]
The relative activity of a species i, denoted a i, is defined [4] [5] as: = where μ i is the (molar) chemical potential of the species i under the conditions of interest, μ o i is the (molar) chemical potential of that species under some defined set of standard conditions, R is the gas constant, T is the thermodynamic temperature and e is the exponential constant.
The Gibbs adsorption isotherm for multicomponent systems is an equation used to relate the changes in concentration of a component in contact with a surface with changes in the surface tension, which results in a corresponding change in surface energy. For a binary system, the Gibbs adsorption equation in terms of surface excess is
In solution chemistry and biochemistry, the Gibbs free energy decrease (∂G/∂ξ, in molar units, denoted cryptically by ΔG) is commonly used as a surrogate for (−T times) the global entropy produced by spontaneous chemical reactions in situations where no work is being done; or at least no "useful" work; i.e., other than perhaps ± P dV.