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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 electricity and gravity, [3] [4], or to fluids in porous media. [5] The equation is named after Josiah Willard Gibbs and Pierre Duhem.
The Duhem–Margules equation, named for Pierre Duhem and Max Margules, is a thermodynamic statement of the relationship between the two components of a single liquid where the vapour mixture is regarded as an ideal gas:
The Margules activity model is a simple thermodynamic model for the excess Gibbs free energy of a liquid mixture introduced in 1895 by Max Margules. [1] [2] After Lewis had introduced the concept of the activity coefficient, the model could be used to derive an expression for the activity coefficients of a compound i in a liquid, a measure for the deviation from ideal solubility, also known as ...
Which is the Gibbs–Duhem relation. The Gibbs–Duhem is a relationship among the intensive parameters of the system. It follows that for a simple system with I components, there will be I + 1 independent parameters, or degrees of freedom. For example, a simple system with a single component will have two degrees of freedom, and may be ...
The Duhem–Margules equation and the Margules' Gibbs free energy equation are examples of his free-time devotion. In 1900 his interest switched to meteorology and where he found great success by deploying his thermodynamic knowledge. This led to the Margules formula, a formula for characterizing the slope of a front. He dedicated his ...
Thus, they are essentially equations of state, and using the fundamental equations, experimental data can be used to determine sought-after quantities like G (Gibbs free energy) or H . [1] The relation is generally expressed as a microscopic change in internal energy in terms of microscopic changes in entropy , and volume for a closed system in ...
Notice that the Margules function for each component contains the mole fraction of the other component. It can also be shown using the Gibbs-Duhem relation that if the first Margules expression holds, then the other one must have the same shape. A regular solutions internal energy will vary during mixing or during process.
In thermodynamics, an activity coefficient is a factor used to account for deviation of a mixture of chemical substances from ideal behaviour. [1] In an ideal mixture, the microscopic interactions between each pair of chemical species are the same (or macroscopically equivalent, the enthalpy change of solution and volume variation in mixing is zero) and, as a result, properties of the mixtures ...