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Raoult's law (/ ˈ r ɑː uː l z / law) is a relation of physical chemistry, with implications in thermodynamics.Proposed by French chemist François-Marie Raoult in 1887, [1] [2] it states that the partial pressure of each component of an ideal mixture of liquids is equal to the vapor pressure of the pure component (liquid or solid) multiplied by its mole fraction in the mixture.
The simplest definition is that an ideal solution is a solution for which each component obeys Raoult's law = for all compositions. Here p i {\displaystyle p_{i}} is the vapor pressure of component i {\displaystyle i} above the solution, x i {\displaystyle x_{i}} is its mole fraction and p i ∗ {\displaystyle p_{i}^{*}} is the vapor pressure ...
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 ...
For instance, for solutions of magnesium chloride, the vapor pressure is slightly greater than that predicted by Raoult's law up to a concentration of 0.7 mol/kg, after which the vapor pressure is lower than Raoult's law predicts. For aqueous solutions, the osmotic coefficients can be calculated theoretically by Pitzer equations [4] or TCPC model.
In contrast to ideal solutions, regular solutions do possess a non-zero enthalpy of mixing, due to the W term. If the unlike interactions are more unfavorable than the like ones, we get competition between an entropy of mixing term that produces a minimum in the Gibbs free energy at x 1 = 0.5 and the enthalpy term that has a maximum there.
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 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 ...
The Modern Theory of Solutions: Memoirs by Pfeffer, Van't Hoff, Arrhenius, and Raoult. New York: Harper and Brothers. (Contains reprints of three papers by Raoult) General Law of the Freezing of Solutions (Comptes Rendus 95, 1030 - 1033, 1882) General Law of the Vapor Pressure of Solvents (Comptes Rendus 104, 1430 - 1433, 1887)